Synthesis and ROMP Chemistry of
Decafluoroterphenoxide Molybdenum Imido Alkylidene
and Ethylene Complexes
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Citation
Yuan, Jian, Richard R. Schrock, Laura C. H. Gerber, Peter
Müller, and Stacey Smith. “Synthesis and ROMP Chemistry of
Decafluoroterphenoxide Molybdenum Imido Alkylidene and
Ethylene Complexes.” Organometallics 32, no. 10 (May 24,
2013): 2983–2992.
As Published
http://dx.doi.org/10.1021/om400199u
Publisher
American Chemical Society
Version
Author's final manuscript
Accessed
Wed May 25 19:07:22 EDT 2016
Citable Link
http://hdl.handle.net/1721.1/86910
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Detailed Terms
Synthesis and ROMP Chemistry of
Decafluoroterphenoxide Molybdenum Imido
Alkylidene and Ethylene Complexes
Jian Yuan, Richard R. Schrock*, Laura C. H. Gerber, Peter Müller, and Stacey J. Smith
Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts Institute 02139, United
States
KEYWORDS (Word Style “BG_Keywords”). If you are submitting your paper to a journal that requires keywords, provide
significant keywords to aid the reader in literature retrieval.
ABSTRACT: BisDFTO alkylidene complexes of molybdenum Mo(NR)(CHCMe2Ph)(DFTO)2 (R = 2,6-i-Pr2C6H3, 2,6-Me2C6H3,
C6F5, and 1-Adamantyl; DFTO = 2,6-(C6F5)2C6H3O) and monoaryloxide monopyrrolide (MAP) complexes
Mo(NR)(CHCMe2Ph)(Me2Pyr)(OAr) (Me2Pyr = 2,5-dimethylpyrrolide; R = C6F5, OAr = DFTO or 2,6-dimesitylphenoxide
(HMTO); R = 2,6-Me2C6H3, OAr = DFTO) have been prepared in good yields. Addition of dicarbomethoxynorbornadiene
(DCMNBD) to bisDFTO complexes yielded polymers that have a cis,isotactic structure. Polymerization of DCMNBD by
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO) gives a polymer that contains the expected cis,syndiotactic structure, but polymerization
of DCMNBD by Mo(NR)(CHCMe2Ph)(Me2Pyr)(DFTO) (R = C6F5 or 2,6-Me2C6H3) generates a polymer that has a cis,isotactic
structure, the first observation of a cis,isotactic polymer prepared employing a MAP initiator. Norbornene is polymerized to give
what is proposed to be highly tactic cis-polyNBE. Addition of ethylene to Mo(NC6F5)(CHCMe2Ph)(DFTO)2 leads to formation of
Mo(NC6F5)(CH2CH2)(DFTO)2, which also behaves as an initiator for polymerization of DCMNBD to cis,isotactic-polyDCMNBD
and norbornene to cis highly tactic polyNBE. Mo(NC6F5)(CH2CH2)(DFTO)2 reacts with 3-methyl-3-phenylcyclopropene (MPCP)
to give Mo(NC6F5)(CHCHCMePh)(DFTO)2 in ~50% yield.
INTRODUCTION
Olefin metathesis is of continuing importance to the
synthesis of organic molecules and polymers, both as a consequence of its very nature, i.e., the synthesis of C=C bonds
catalytically from C=C bonds, and because of the control that
can be exercised through the use of well-defined Mo, W, and
Ru complexes as catalysts for that reaction.1 In the interest of
exploring variations of Mo and W olefin metathesis complexes
that contain an electron withdrawing imido ligand, we recently
devised routes to pentafluorophenylimido alkylidene
complexes.2 We were especially interested in exploring high
oxidation state MonoAryloxide Pyrrolide (MAP) imido alkylidene complexes of Mo and W for Z-selective olefin metathesis
reactions.3
In the process we introduced the 2,6bis(pentafluorophenyl)phenoxide (decafluoroterphenoxide or
DFTO) ligand, a sterically demanding but more electron withdrawing terphenoxide than either HMTO (O-2,6-(2,4,6Me3C6H3)2C6H3) or HIPTO (O-2,6-(2,4,6-i-Pr3C6H3)2C6H3),
and one that also is unlikely to be subject to any CH activation
within the ligand. We failed to make MAP complexes that
contain the DFTO ligand through protonation of bispyrrolide
precursors as a consequence of "overprotonation" to yield
M(NC6F5)(CHCMe2Ph)(DFTO)2 complexes.
However,
M(NC6F5)(CHCMe2Ph)(DFTO)2 complexes attracted our
attention because analogous bisHMTO or bisHIPTO have not
been prepared, and because M(NC6F5)(CHCMe2Ph)(DFTO)2
initiates polymerization of 2,3-dicarbomethoxynorbornadiene
(DCMNBD) to give poly(DCMNBD) with a structure that is
>99% cis and isotactic, a result that is not known for bisalkoxide or bisaryloxide imido alkylidene complexes.4 In this paper
we report the synthesis of new MAP complexes that contain
the DFTO ligand along with a more thorough exploration of
reactions of bisDFTO complexes that are relevant to ROMP
reactions. This exploration includes the synthesis and chemistry of the ethylene complex, Mo(NC6F5)(CH2CH2)(DFTO)2,
and a study of its behavior as an initiator for ROMP.
RESULTS AND DISCUSSION
Synthesis of BisDFTO Mo complexes.
Treatment of Mo(NR)(CHCMe2Ph)(OTf)2(DME) complexes with two equivalents of DFTOLi (LiO-2,6(C6F5)2C6H3) at -30 oC in toluene gave the bisDFTO
complexes, Mo(NR)(CHCMe2Ph)(DFTO)2 (1a-1d; R = 2,6-iPr2C6H3, 2,6-Me2C6H3, C6F5, and 1-adamantyl; equation 1).
These complexes also can be prepared through addition of two
equivalents of DFTOH to Mo(NR)(CHCMe2Ph)(Me2Pyr)2 in
diethyl ether at room temperature. We attribute the failure to
prepare Mo(NR)(CHCMe2Ph)(OR)2 by either method when
OR is HIPTO or HMTO to a higher pKa for HIPTOH or
HMTOH and therefore slower protonation of pyrrolide
ligands, or to side reactions that involve deprotonation of the
alkylidene5 when Mo(NR)(CHCMe2Ph)(OTf)2(DME) is
treated with aryloxide salts.
In 19F NMR spectra of 1a-1d at 20 °C, one para, two
meta and two ortho fluorine DFTO resonances are observed
(Figure 1). The presence of two meta and two ortho
resonances is consistent with hindered rotation of the C 6F5 ring
about the C-C connection between C6F5 rings and the central
phenyl ring, but free rotation about the Mo-O bonds on the
NMR time scale. The 19F NMR spectrum of 1c at -80 oC
reveals resonances (some overlapping) for eight DFTO ortho
fluorines, eight meta fluorines, and four para fluorines, consistent with no molecular symmetry for 1c on the NMR time
scale at that temperature. An X-ray structure2 revealed that the
two DFTO ligands are oriented approximately perpendicular
to each other to give an enantiomorphic atropisomer in the
solid state. The DFTO ligands in the atropisomer resemble the
two halves of a baseball cover with the basic C2 symmetry
being reduced to Cs as a consequence of the presence of the
imido and alkylidene ligands. We propose that the atropisomeric form leads to the inequivalence of all twenty DFTO
fluorines on the NMR time scale. Rotation of the two DFTO
ligands past one another and past the imido and alkylidene
ligands creates a mirror plane on the NMR time scale at higher
temperatures that coincides with the Nimido-Mo-C plane.
Synthesis of MAP complexes
Treatment of Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 with one
equivalent of 2,6-dimesitylphenol (HMTOH) at 70 oC for 16 h
led
to
formation
of
the
MAP
complex
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO) in 60% yield
(equation 2). However, addition of one equivalent of DFTOH
to Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 at 22 °C or -30 oC in
toluene followed by warming the sample to 20 °C, produced a
mixture
of
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2,
Figure 1. Variable temperature 19F NMR spectra of 1c (in toluene-d8).
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(DFTO)
(2b),
and
Mo(NC6F5)(CHCMe2Ph)(DFTO)2 (1c) (~1:1:1 through
integration of alkylidene resonances). In contrast, when reactions between Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 and DFTOH
were
carried
out
in
acetonitrile,
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(DFTO)(MeCN) (2b') could
be isolated as an orange solid in 75% yield. Proton NMR
studies suggest that the acetonitrile in 2b' dissociates readily;
indeed, it can be removed by dissolving 2b' in toluene and
removing the toluene and acetonitrile in vacuo in several
cycles. Compound 2b was obtained as a red-orange solid that
could be recrystallized from a mixture of diethyl ether and
pentane.
We propose that in the reaction between
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 and DFTOH acetonitrile is
a good enough ligand to prevent overprotonation since the
oxygen of DFTOH must bind to the metal before the proton
can transfer to the pyrrolide ligand. Fortunately, acetonitrile is
also a poor enough ligand in this situation to be removed from
2b' in vacuo.
An X-ray study of 2b' revealed it to have a square pyramidal structure (τ = 0.067; τ = 0 for a perfect square pyramid6)
Figure 2. Thermal ellipsoid plot of the structure of 2b'. Hydrogen atoms
have been omitted for clarity. Selected bond distance (Å) and angles
(deg): Mo(1)-N(1) = 1.751(1), Mo(1)-C(1) = 1.889(1), Mo(1)-O(1) =
1.995(1), Mo(1)-N(2) = 2.084(1), Mo(1)-N(3) = 2.190 (1), C(11)-N(1) =
1.378(1); O(1)-C(31) = 1.336(1); N(1)-Mo(1)-O(1) = 154.35 (4), N(2)Mo(1)-N(3) = 158.37(4).
with the alkylidene in the apical position and acetonitrile
bound trans to the dimethylpyrrolide (Figure 2). The Mo(1)N(1) (1.751(1)Å) and the Mo(1)-C(1) (1.889(1)Å) distances
are similar to those found in other square pyramidal MAP
adducts that contain PMe3 or THF.7 The alkylidene is found
in the apical position of the square pyramid in all crystallographically characterized MAP adducts so far.
Synthesis of a Molybdenum Ethylene Complex.
Reaction of a new alkylidene complex with ethylene is a
relatively routine means of exploring the ease of formation
and stability of methylidene and unsubstituted metallacyclobutane complexes.
Exposure
of
a
diethyl
ether
solution
of
Mo(NC6F5)(CHCMe2Ph)(DFTO)2 (1c) to 1 atm of ethylene at
room temperature led to a color change from orange to deep
purple over a period of 16 h and formation of the ethylene
complex, Mo(NC6F5)(CH2CH2)(DFTO)2 (3; equation 3), in 76%
yield. At room temperature the 1H NMR spectrum for 3 in
tol-d8 showed two ethylene proton resonances at 1.33 and 2.48
ppm (Figure 3). At -80 oC these two resonances split into four
at δ 0.81, 1.85, 2.19 and 2.60 ppm. The 19F NMR spectrum of
3 at -80 oC reveals resonances for eight ortho fluorines, eight
meta fluorines, and four para fluorines for the two DFTO
ligands, as found for 1c (Figure 1). All data are consistent
with 3 having no symmetry at -80 oC on the NMR time scale,
as found for 1c.
The structure of 3 as determined through a single-crystal
X-ray diffraction study is shown in Figure 4. The Mo1-C2
bond length (2.140(4) Å) is essentially the same as the
These structural features are similar to those observed for the
four other Mo imido ethylene complexes in the literature.8
When 1c was treated with 13CH2=13CH2 in C6D6 and the
reaction followed by 13C NMR, 1c was fully converted into a
mixture
of
a
TBP
metallacyclobutane
complex,
Mo(NC6F5)(13CH213CH213CH2)(DFTO)2
(4*),
and
13
CH2=CHCMe2Ph in 5 min. After 15 min, resonances for
Mo(NC6F5)(13CH213CH2)(DFTO)2 (3*) and 13CH2=13CH13CH3
could be observed; after 24 h conversion to 3* and
13
CH2=13CH13CH3 was complete. According to proton NMR
spectra the amount of propylene was less than one equivalent
Figure 4. Thermal ellipsoid plot of 3. Hydrogen atoms have been omitted
for clarity. Selected bond distance (Å) and angles (deg): Mo(1)-N(1) =
1.720(3), Mo(1)-O(2) = 1.935(3), Mo(1)-O(1) = 1.946(3), Mo(1)-C(2) =
2.140(4), Mo(1)-C(1) = 2.153(4), C(1)-C(2) = 1.415(6); N(1)-Mo(1)-O(2)
= 121.37(14), N(1)-Mo(1)-O(1) = 114.79(14), O(2)-Mo(1)-O(1) =
108.45(11), C(2)-Mo(1)-C(1) = 38.49(15), C(2)-C(1)-Mo(1) = 70.3(2),
C(1)-C(2)-Mo(1) = 71.2(2).
Mo1-C1 bond length (2.153(4) Å). The C1-C2 bond distance is 1.415(6)Å and the C1-Mo1-C2 angle is 38.49(15)o.
Figure 5. 13C NMR spectrum of Mo(NC6F5)( 13CH2=13CH2)(DFTO)2 and
CH2=13CH2 in C6D6 at room temperature ([Mo] = Mo(NC6F5)(DFTO)2).
13
Figure 3. Variable temperature 1H NMR spectra of 3 (tol-d8).
The C1-C2 bond is essentially perpendicular to the Mo1-N1
bond (N1-Mo1-C1 = 97.00(15); N1-Mo1-C2 = 96.00(16).
as a consequence of some being lost into the head space. A
13
C NMR spectrum of isolated 3* under ~0.5 atm of
13
CH213CH2 at room temperature showed that two carbon
resonances were present at δ 82.9 and 39.9 ppm (with a second
order coupling pattern), consistent with formation of a small
amount
of
the
metallacyclopentane
complex,
Mo(NC6F5)(13CH213CH213CH213CH2)(DFTO)2 (~2%; Figure
5).9 We propose that Mo(NC6F5)(13CH213CH213CH2)(DFTO)2
rearranges to Mo(NC6F5)(13CH2=13CH13CH3)(DFTO)2 and that
propylene is then displaced (most likely) by ethylene to give
Mo(NC6F5)(13CH213CH2)(DFTO)2 and free propylene. The
mechanism of rearrangement is proposed to consist of
hydride elimination in the metallacyclobutane complex to
give an intermediate allyl hydride followed by reductive
elimination. Formation of an alkyl intermediate through CH
activation in either the DFTO or the NC6F5 ligands is not possible. However, migration of the hydride in the metallacyclobutane to the imido nitrogen to give an intermediate
Mo(IV) complex, Mo(NHC6F5)(13CH213CH13CH2)(DFTO)2,
cannot be ruled out.
Polymerization of DCMNBD Initiated by 1
We
often
employ
polymerization
of
2,3dicarbomethoxynorbornadiene (DCMNBD) as a means of
assessing the potential stereoselectivity of a given initiator.
We noted in the communication that DCMNBD was polymerized by initiator 1c to give cis,isotactic polymer.2 Addition of
100 equivalents of DCMNBD to 1a-d also led to the formation
of poly(DCMNBD). As shown in Table 1 only initiators 1b
and 1c produce a polymer with a highly regular >98 % cis,
>98% isotactic structure, on the basis of the chemical shift of
the methylene carbon (C(7)) at 38.7 ppm in CDCl3;10 this contrasts with a chemical shift for C(7) of 38.0 ppm in
cis,syndiotactic poly(DCMNBD).3b Formation of cis,isotactic
poly(DCMNBD) employing an imido alkylidene bisalkoxide
initiator is not known.4
However, polymerization of
DCMNBD
initiated
by
W(CH-t-Bu)(O)(O-2,6Ph2C6H3)2(PPh2Me) has been reported to produce >95% cis,
>95% isotactic poly(DCMNBD).11 Initiators that contain chiral biphenolate and binaphtholate ligands produce cis,isotactic
poly(DCMNBD) through enantiomorphic site control.4 Only
atactic polymer was formed employing initiator 1d, either
isolated or prepared in situ. The lower efficiency of forming a
cis,isotactic polymer with initiator 1a is likely to
be a consequence of too much steric hindrance.
Table 1. Poly(DCMNBD) formed employing
Mo(NR)(CHCMe2Ph)(DFTO)2 initiators.
Cmpd
1a
1b
1c
1d
R
2,6-i-Pr2C6H3
2,6-Me2C6H3
C6F5
Adamantyl
% cis
89
>98
>98
% tacticity
72 iso
>98 iso
>98 iso
atactic
GPC analyses of cis,isotactic poly(DCMNBD) made
from 50, 100, 200 and 800 equivalents of DCMNBD in CHCl3
at room temperature with initiator 1c (Table 2) showed that the
polydispersity of each sample is relatively low and decreases
as the polymer length increases, both of which suggest that the
polymerization is relatively well-behaved. (For a neophylidene initiator kp often is greater than ki and PDI values therefore are higher than when kp and ki are comparable.) The
relationship between the number of equivalents of monomer
employed and the number average molecular weight of the
Table 2. GPC studies of Poly(DCMNBD) prepared with 1c as the initiator
(Mn in CHCl3 vs. Polystyrene; n = equiv of monomer added).
n
conversion (%)
Mn
PDI
50
>98
7000
1.19
100
>98
13000
1.17
200
>98
24000
1.15
800
>98
88000
1.10
polymers measured in CHCl3 versus polystyrene standards is
linear with an R2 value 0.9999 (Figure S1 in SI).
Polymerization of DCMNBD by bisDFTO initiators 1b or
1c to yield cis,isotactic poly(DCMNBD) would seem to require that the monomer attack the same side of a M=C bond in
each step.
We tentatively suggest that cis,isotactic
poly(DCMNBD) forms through a type of chain end control
where one diastereomer is created through interlocking of the
terphenoxide ligands in combination with the chirality of the
last inserted monomer; reaction of the other diastereomer is
not competitive. The failure of 1d to yield cis,isotactic
poly(DCMNBD) suggests that the nature of the imido group is
a significant part of the puzzle that is not yet understood.
Polymerization of DCMNBD Initiated by 2a-2c
Addition of 100 equivalents of DCMNBD to 2a led to
consumption of the monomer and formation of polymer within
30 min. The polymer is >98% cis,syndiotactic (Table 3), as is
the
poly(DCMNBD)
produced
employing
Mo(NAd)(CHCMe2Ph)(Pyr)(OHIPT)3b as an initiator. The
polymer obtained with 2b' is largely cis but relatively atactic,
presumably solely as a consequence of the presence of one
equivalent of acetonitrile. To our surprise, treatment of 2b
with 100 equivalents of DCMNBD led to the formation of a
new polymer that has a 95% cis and 91% isotactic structure,
while poly(DCMNBD) prepared with 2c as the initiator was
Table 3. Poly(DCMNBD) formed with initiators
Mo(NR)(CHCMe2Ph)(Me2Pyr)(OAr) (2a-2c).
initiator
R
ArO
cis (%)
2a
C6F5
HMTO
>98
Tacticity
2b'
C6F5
DFTO
92
2b
C6F5
DFTO
95
91% iso
2c
2,6-Me2C6H3
DFTO
>98
96% iso
>98% syndio
atactic
was found to contain ~98% cis and 96% isotactic dyads.
Formation of cis,isotactic polymer with a MAP initiator has
never been observed although formation of trans,isotacticpoly[(+)-2,3-dicarbomethoxynorbornene] employing a MAP
initiator has been reported recently.3l The change in tacticity
upon changing from HMTO (in 2a) to DFTO (in 2b) is
striking, as is the disruption of the tacticity of the
poly(DCMNBD) in the presence of one equivalent of acetonitrile (in 2b').
Table 4. GPC studies of Poly(DCMNBD) Samples using 2b as an initiator
(Mn in CHCl3 vs. Polystyrene; n = equiv of monomer added; n' = the required equiv of monomer to produce the same Mn with initiator 1c).
n
conversion (%)
Mn
PDI
n'
n/n'
50
>99
28000
1.19
242
0.21
100
>99
55000
1.20
490
0.20
200
>99
90000
1.26
817
0.24
Poly(DCMNBD) made from 50, 100 and 200 equivalents
of monomer in CHCl3 with initiator 2b were analyzed by GPC
(Table 4). Compared to the polymer produced by initiator 1c
(Table 2), the polydispersities of each of the samples is
relatively high and increases as the polymer length increases.
The relationship between the number of equivalents of monomer employed and the number average molecular weight of
the polymers measured in CHCl3 versus polystyrene standards
is also linear with an R2 value 0.99 (Figure S2 in SI). The
molecular weights of these polymers are about five times what
they are when 1c is employed as the initiator, as can be seen
from the data in Table 2; the ratio of n/n' is ~0.2, where n'
would be the required number of equivalents to produce an
observed Mn employing initiator 1c.
Formation of largely cis,isotactic-poly(DCMNBD) by 2b
and 2c contrasts dramatically with the cis,syndiotacticpoly(DCMNBD) formed when 2a is employed as an initiator.
In fact, we can explain formation of cis,isotacticpoly(DCMNBD) only if the "rule" concerning approach of the
monomer trans to a pyrrolide ligand does not hold in this
situation, or if we invoke a turnstile rotation of a metallacyclobutane intermediate followed by a rotation of the alkylidene
ligand, as shown in Scheme 1. We have entertained the possibility that a propagating species generated from 2b disproportionates to yield bispyrrolide and bisDFTO complexes and that
the cis,isotactic structure arises through selective polymerization of DCMNBD by the bisDFTO complex so formed. However, a mixture of 1c and Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2
(1:1) in C6D6 did not give any 2b at room temperature or upon
heating to 50 oC for 16 h. Also, the data in Table 4 would
suggest that the amount of disproportionation would have to
be
~20%.
It
should
be
noted
that
Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OC6F5) has been found to
yield a mixture of Mo(NAr)(CHCMe2Ph)(Me2Pyr)2 plus
Mo(NAr)(CHCMe2Ph)(OC6F5)2 in solution.12 We conclude
that disproportionation of a propagating species generated
from 2b cannot be rejected out of hand, but it seems unlikely
at this stage.
ROMP initiated by Mo(NC6F5)(CH2CH2)(DFTO)2 (3).
When Mo(NC6F5)(CH2CH2)(DFTO)2 was treated with 50
equivalents of DCMNBD in CDCl3 in a J. Young tube, a trace
amount of polymer was observed after 16 hours at room temperature. Upon heating the reaction for 4 hours at 50 oC, 48%
of the monomer was consumed. The reaction was monitored
by 1H NMR and conversion vs. time is shown in Figure 6. All
monomer was consumed after 16 hours at 50 oC in a Schlenk
flask when ethylene was removed in a flow of nitrogen gas.
13
C NMR analysis of the poly(DCMNBD) showed that the
polymer is >99% cis and isotactic. The same phenomenon
was observed when 1% catalyst was employed, even when
samples of 3 were exposed multiple times to ethylene and
recovered. Therefore the evidence argues against the possibility that the polymerization can be ascribed to a trace of residual alkylidene complex. Since cis,isotactic poly(DCMNBD) is
formed employing Mo(NC6F5)(CHCMe2Ph)(DFTO)2 as an
initiator, it seems highly likely that the initiator for the
polymerization is a bisDFTO complex and that the initiator is
generated from DCMNBD itself.
Addition of one equivalent of DCMNBD to
Mo(NC6F5)(CH2CH2)(DFTO)2 led to formation of a redorange crystalline product in 57% yield with the apparent
composition Mo(NC6F5)(CH2CH2)(DCMNBD)(DFTO)2 (5).
Figure 6. Consumption of DCMNBD in CDCl3 by 3 at 50 °C. Blue diamonds imply 2% catalyst loading, green triangles imply 1% catalyst loading, red squares and purple crosses are 1% catalyst loading with 3 that had
been exposed to ethylene to remove any alkylidene impurities.
The 1H NMR spectrum showed four triplet of doublet
resonances (12 Hz, 4 Hz) at δ 1.43, 1.77, 2.72 and 3.07 ppm
for the ethylene protons, which is indicative of a product with
no symmetry. An X-ray diffraction study showed that the
DCMNBD has bonded to Mo through the carbonyl groups in
the two esters (Figure 7), rather than forming a "mixed" metallacyclopentane from DCMNBD and ethylene. One ester is
trans to the ethylene ligand while the other is trans to the imido group. The two DFTO ligands are trans to each other.
The bond lengths and angles are unsurprising. The Mo1-C1
distance (2.187(1)Å) is slightly shorter than the Mo1-C2
distance (2.195(1)Å) and the C1-C2 distance is 1.416(2)Å).
Figure 7. Thermal ellipsoid plot of 5. Hydrogen atoms have been omitted
for clarity. Selected bond distance (Å) and angles (deg): C(1)-C(2) =
1.416(2), Mo(1)-C(1) = 2.187(1), Mo(1)-C(2) = 2.195(1), Mo(1)-N(1) =
1.7290(9), Mo(1)-O(1) = 2.1983(8), Mo(1)-O(3) = 2.2198(8), Mo(1)O(5) = 2.0664(7), Mo(1)-O(6) = 2.1041(7); N(1)-Mo(1)-O(3) = 178.92(4),
O(5)-Mo(1)-O(6) = 148.94(3), C(1)-Mo(1)-C(2) = 37.70(4).
The synthesis of six-coordinate 5 suggests that the steric
limits associated with, or imposed by, two terphenoxide
ligands are difficult to predict, although the electronwithdrawing DFTO ligands should encourage adduct for-
mation. It also should be noted that bisaryloxide catalysts
have been employed in macrocyclizations that give trisubstituted double bonds,3k which suggests that crowded bisaryloxide catalysts may turn out to have some special properties in
metathesis reactions that have been overlooked. In any case,
coordination of the esters in DCMNBD to the metal almost
certainly impedes formation of an initiator from DCMNBD.
Addition of 100 equivalents of DCMNBD to
Mo(NC6F5)(13CH213CH2)(DFTO)2 led to the formation of
~50% yield of polymer in 8 h at 50 °C in CDCl3. The 13C
NMR spectra exhibit one 13C resonance at δ 116.1 ppm along
with others expected for naturally abundant 13C in the polymer. A 2D 13C-1H HMBC experiment (Figure S3) confirmed
that the 13C resonance at 116.1 ppm is that in a PCH=13CH2
group (P = polymer) at one end of the poly(DCMNBD); the
magnitudes of the coupling of the two protons in the 13CH2
group to a third olefinic proton were found to be 17 Hz (Jtrans)
and 7 Hz (Jcis). We propose, in part on the basis of results to
be described later, that the PCH=13CH2 group results from a
back reaction between liberated 13CH213CH2 and a growing
polymer
chain,
not
through
formation
of
Mo(NC6F5)(13CH2)(DFTO)2 as the initiator.
Addition of 100 equivalents of norbornene to 3 at room
temperature led to formation of poly(norbornene) in seconds.
The 13C NMR spectrum of the polymer in CDCl3 showed only
four sharp resonances (at 134.00, 42.83, 38.72, and 33.34
ppm), characteristic of pure cis poly(NBE).13 Samples prepared with initiators 1c or 2a were identical to those prepared
with initiator 3. The widths of the resonances at half height
are ~9 Hz at 125 MHz, which are unusually narrow. It seems
unlikely, but not impossible, that the samples made with 1c or
2a are each highly tactic but have different tacticities (expected to be iso and syndio, respectively), since at least one
additional resonance in a 125 MHz 13C NMR experiment,
most likely near the one at 38.72 ppm, should be present if
polymers with two different tacticities are formed. In early
work on poly(NBE) 13C NMR spectra,13 Ivin and coworkers
decided that fine structure due to tacticity differences, at least
in the relatively low frequency 13C NMR experiments at that
time, could not be detected. However, a second explanation of
the result obtained here is that the cis highly tactic poly(NBE)
samples produced with initiators 1c and 2a are both isotactic.
This possibility would require that the "rule" concerning formation of syndiotactic polymers with HMTO MAP species
breaks down for norbornene, just as it did when cis,isotactic
poly(DCMNBD) was formed with initiators 2b or 2c. Whether the tacticity of poly(NBE) is iso or syndio cannot be determined through NMR studies since no chiral element is present
in the polymer.4 As far as we are aware, this is the first time
that pure >98% cis and (we propose) highly (>98%) tactic
poly(norbornene) has been prepared.
Addition of one equivalent of norbornene to
Mo(NC6F5)(13CH213CH2)(DFTO)2 at -78 oC in toluene-d8
showed that after 1h at -70 °C, 69% of the ethylene complex
was converted to the "mixed" metallacyclopentane complex 6
(eq 4). The 13CH2 resonances in the metallacycle were
observed as first order doublets at δ 84.7 and 46.6 ppm (1Jcc=
37 Hz) in the 13C NMR spectrum at -70 oC, consistent with
one isomer of 6 being formed. When the temperature was
raised to -50 oC, the concentration of 6 decreased while the
concentration of 3 and poly(norbornene) increased. After 1
hour at -50 oC, all the norbornene had been consumed and the
ethylene complex 3 was observed as the only Mo species to
contain a 13C label, i.e., no PCH=13CH2 group was detected in
this experiment. As in reactions between 3 and DCMNBD,
ethylene does not appear to be involved in formation of the
initiator.
Treatment of 3 with one equivalent of a mixture of
labeled and unlabeled 3-methyl-3-phenylcyclopropene
(MPCP; two parts of unlabeled MCPC to one part in which
one CH is 13C labeled) at -78 oC led to an immediate color
change from purple to orange and formation of
Mo(NC6F5)(CHCH=CMePh)(DFTO)2 (7; eq 5) upon warming
the sample to room temperature.
Since 1/3 of the
MPCP was monolabeled with 13C in an olefinic position, the
alkylidene proton resonance consists of a doublet at δ 12.10
ppm (d, 3JHH = 9 Hz) along with two 13C satellites (1JCH = 130
Hz, 3JHH = 9 Hz) in a ratio of 1:4:1 (Figure 8), consistent with
7
being
a
mixture
of
[Mo]=13CHCH=C(Me)Ph,
13
[Mo]=CH CH=C(Me)Ph, and [Mo]=CHCH=C(Me)Ph in one
isomeric form (where [M] = Mo(NC6F5)(DFTO)2). (The isomer shown in equation 6 is arbitrary.) A similar coupling pattern was observed for the β-hydrogen at δ 8.33 ppm (1JCH =
159 Hz, 3JHH = 9 Hz). The origin of the minor resonances at
12.20 ppm, 8.65 ppm, and 8.15 ppm (inter alia) has not been
identified. In the 13C NMR spectrum, the alkylidene carbon
resonance was found at δ 264.5 ppm and the β-carbon
resonance was found at δ 136.0 ppm. The vinyl alkylidene 7
rapidly initiates ROMP of MPCP at -78 °C or room temperature to yield atactic poly(MPCP).3d We propose that MPCP
replaces ethylene in 3 to give a MPCP complex that then
rearranges to form the vinyl alkylidene complex 7. A single
Figure 8. 1H NMR spectrum of 7 in C6D6.
experiment employing 3, unlabeled ethylene, and trimethoxybenzene as an internal standard showed that
Mo(NC6F5)(CHCH=CMePh)(DFTO)2 was formed in 50%
yield. We propose that some MPCP is polymerized in the
process. Ready conversion of 3 into an alkylidene is
analogous to the results of reactions between
3,3-diphenylcyclopropene and complexes that contain Ti(II) or
Zr(II),14 W(IV),15 or Ru(II).16
The ROMP of DCMNBD with 3 to give cis,isotacticpoly(DCMNBD),
strongly
suggests
that
some
Mo(NC6F5)(ODFT)2(CRR') initiator is formed from
DCMNBD. The ROMP of norbornene by 3 also suggests that
some initiator forms from norbornene. These results can be
added to others in the last several years that employ Mo(IV) or
W(IV) initiators for metathesis reactions.17 Evidence in a literature that stretches over several decades suggests that a norbornylidene complex can form from a norbornene via a
1,2-shift of an olefinic hydrogen.18
However, to our
knowledge no pure norbornylidene complex has ever been
prepared.
The closest is formation of a mixture of
(Silox)3M(norbornene) (Silox = t-Bu3SiO; M = Nb, Ta) and
(Silox)3M(norbornylidene) as part of a study of isomerization
of (Silox)3M(alkene) complexes to (Silox)3M(alkylidene)
complexes via formation of intermediate alkyl complexes
through CH activation in a Silox ligand.19
CONCLUSIONS
This first exploration of DFTO alkylidene complexes
suggests that they can behave quite differently than complexes
that contain superficially similar terphenoxides such as
HMTO. Mo(NR)(CHCMe2Ph)(DFTO)2 complexes have no
HMTO or HIPTO analogs and behave in a ROMP reaction as
if the metal were chiral. Some observations can be ascribed to
the electron withdrawing ability of the DFTO ligand in combination with dramatic steric bulk. However, formation of
cis,isotactic poly(DCMNBD) from both MAP initiators 2b
and 2c, as well as apparently identical cis and highly tactic
poly(norbornene) samples employing initiators 1c and 2a,
suggest that the "rule" concerning formation of syndiotactic
polymers from MAP initiators requires rethinking and testing.
Finally, ROMP polymerization initiated by the ethylene
complex 3 appears to proceed via an alkylidene formed from
the monomer itself.
EXPERIMENTAL
General. All manipulations were conducted under a nitrogen
atmosphere in a glovebox under nitrogen or through Schlenk
techniques. All glassware was dried in an oven prior to use.
Ether, pentane, toluene, dichloromethane, toluene, and benzene were degassed with dinitrogen and passed through activated alumina columns under nitrogen. All dried and deoxygenated solvents were stored over molecular sieves in a nitrogen or argon-filled glovebox. NMR spectra were recorded on
a 500 MHz spectrometer. Chemical shifts for 1H spectra were
referenced to the residual 1H resonances of the deuterated solvent (1H NMR C6D6 ppm; CDCl3  7.26 ppm; toluened8
7.09, 7.01, 6.97, 2.08 ppm; 13C NMR
C6D6ppm; CDCl3  77.16 ppm; toluene-d8 20.43
ppm) and are reported as parts per million relative to tetramethylsilane. Midwest Microlab, Indianapolis, IN, provided
elemental analyses. The following abbreviations refer to the
multiplicity: s = singlet, d = doublet, t = triplet, m = multiplet,
br = broad. Others include Ar' = 2,6-Me2C6H3, Ad = 1adamantyl,
and
Ar
=
2,6-i-Pr2C6H3.
Mo(NC6F5)(CHCMe2Ph)(OTf)2(DME),2
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2,2
Mo(NAr')(CHCMe2Ph)(OTf)2(DME),3c
Mo(NAr')(CHCMe2Ph)(Me2Pyr)2,Error! Bookmark not defined.
Mo(NC6F5)(CHCMe2Ph)(DFTO)2,2
Mo(NAd)(CHCMe2Ph)(Me2Pyr)2,7a and DFTOH2 were prepared as described in the literature. All the other reagents
were used as received unless noted otherwise.
Mo(NAr)(CHCMe2Ph)(DFTO)2
(1a).
Mo(NAr)(CHCMe2Ph)(Me2Pyr)2 (100 mg, 0.159 mmol) was
dissolved in benzene (5 mL). DFTOH (136 mg, 0.320 mmol)
was added at room temperature and the mixture was heated at
100 oC for 16 hours. The solvent was removed to give an
orange oily product. The residue was recrystallized from a
mixture of diethyl ether and pentane to give a yellow solid
(174 mg, 87%): 1H NMR (500 MHz, C6D6, 20 oC) δ 11.69 (s,
1H, Mo=CH), 6.97 (m, 3H), 6.84 (d, 8 Hz, 5H), 6.76 (d, 3JHH =
8 Hz, 2H), 6.68 (m, 4H), 1.90 (sept, 3JHH = 7 Hz, 2H), 1.36 (s,
3
JHH = 6 Hz), 0.84 (s, 12H); 19F NMR (282 MHz, C6D6, 20 oC)
δ -137.8 (m, 4F), -139.2 (m, 4F), -154.6 (m, 4F), -161.2 (m,
4F), -161.7 (m, 4F); 13C{1H} NMR (125 MHz, C6D6, 20 oC) δ
288.7 (s, 1C, Mo=C), 164.5, 147.6, 14.7 (d, 1JCF = 252 Hz),
141.4 (d, 1JCF = 250 Hz), 138.3 (d, 1JCF = 254 Hz), 134.8,
133.5, 125.6 (d, 50 Hz), 124.3 (d, 52 Hz), 122.5, 121.2, 118.3,
113.0, 56.8, 29.3, 28.3. Anal. Calcd for C58H30F20MoNO2: C,
55.65; H, 2.81; N, 1.12. Found: C, 55.39; H, 2.93; N, 1.14.
Mo(NAr')(CHCMe2Ph)(DFTO)2
(1b).
Mo(NAr')(CHCMe2Ph)(OTf)2(DME) (Ar' = 2,6-Me2C6H3; 100
mg, 0.121 mmol) was suspended in toluene (5 mL) and the
mixture was cooled to -30 oC. DFTOLi (110.4 mg, 0.255
mmol) was added at -30 oC and the temperature was allowed
to rise to 22 °C. After 1 hour, the solvent was removed in
vacuo and the dark oily residue was extracted with CH2Cl2 and
the solvent was removed again in vacuo. Pentane (2 mL) was
added and the mixture was stirred for 30 min. The resulting
yellow precipitate was filtered off and dried in vacuo; yield
115 mg (79 %) of a yellow solid; 1H NMR (500 MHz, C6D6,
20 oC) δ 11.39 (s, 1H, Mo=CH), 6.91 (d, 3JHH = 7.5 Hz, 4H),
6.83 (d, 3JHH = 7.5 Hz, 2H), 6.75 (d, 3JHH = 7.5 Hz, 2H), 6.72
(m, 3H), 6.54 (t, 3JHH = 7.5 Hz, 2H), 6.43 (d, 3JHH = 7.5 Hz,
2H), 1.49 (s, 6H), 1.02 (s, 6H); 19F NMR (282 MHz, C6D6, 20
o
C) δ -138.9 (d, 3JFF = 23 Hz, 4F), -139.7 (d, 3JFF = 23 Hz, 4F),
-154.7 (t, 3JFF = 23 Hz, 4F), -161.7 (m, 4F), -162.0 (m, 4F);
13
C{1H} NMR (125 MHz, C6D6, 20 oC) δ 286.0 (s, 1C,
Mo=C), 164.7, 156.3, 147.3, 144.7 (dm, 1JCF = 249 Hz), 141.5
(dm, 1JCF = 252 Hz), 138.3 (dm, 1JCF = 252 Hz), 135.9, 125.5,
121.7, 117.8, 112.7 (m), 55.2, 29.5, 17.5. Anal. Calcd for
C54H27F20MoNO2: C, 54.15; H, 2.27; N, 1.17. Found: C, 53.83;
H, 1.96; N, 0.99.
Mo(NAd)(CHCMe2Ph)(DFTO)2
(1d).
Mo(NAd)(CHCMe2Ph)(Me2Pyr)2 (100 mg, 0.177 mmol) was
suspended in diethyl ether (5 mL). DFTOH (151 mg, 0.354
mmol) was added at room temperature. After 1 hour, the solvent was removed to give yellow oil. Pentane (1 mL) was
added and the mixture was stirred for 30 min. The yellow
precipitate was filtered off and dried in vacuo to give yellow
solid (190 mg, 88%): 1H NMR (500 MHz, C6D6, 20 oC) δ
11.08 (s, 1H, Mo=CH), 7.02 (m, 6H), 6.92 (t, 3JHH = 12 Hz,
1H), 6.77 (t, 3JHH = 12 Hz, 2H), 6.58 (d, 3JHH = 12 Hz, 2H),
1.57 (s, 2H), 1.14 (s, 6H), 1.08 (s, 6H), 0.97 (s, 6H); 19F NMR
(282 MHz, C6D6, 20 oC) δ -139.6 (m, 4F), -140.1 (m, 4F),
-155.1 (t, 3JFF = 21 Hz, 4F), -162.1 (m, 4F), -162.5 (m, 4F);
13
C{1H} NMR (125 MHz, C6D6, 20 oC) δ 280.0 (s, 1C,
Mo=C), 162.967, 149.5, 144.7 (d, 1JCF = 247 Hz), 141.4 (d,
1
JCF = 254 Hz), 138.2 (d, 1JCF = 247 Hz), 133.7(m), 126.5,
121.6, 117.8, 115.0, 112.7, 78.8, 53.1, 50.1, 43.6 (m), 35.1(m),
31.6, 29.7 (m). Anal. Calcd for C56H33F20MoNO2: C, 54.78;
H, 2.71; N, 1.14. Found: C, 54.82; H, 2.61; N, 1.20.
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO)
(2a).
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 (300 mg, 0.502 mmol) was
dissolved in bezene (5 mL). HMTOH (183 mg, 0.557 mmol)
was added and the mixture was heated to 70 oC. After 16 h,
the solvent was removed in vacuo to give a dark colored oily
product. The residue was recrystallized from a mixture of
pentane and diethyl ether to give an orange solid; yield 259
mg (60%): 1H NMR (500 Hz, C6D6, 20 oC)  11.08 (s, 1H,
Mo=CH), 7.24 (d, 3J = 8 Hz, 2H), 6.94 (m, 3H), 6.88(m, 2H),
6.79 (s, 2H), 6.73 (s, 2H), 6.69 (m, 1H), 6.07 (s, 2H), 2.05 (d, J
= 10.5 Hz, 12H), 1.98 (br, 12H), 1.36 (d, J = 11.3 Hz, 6H); 19F
NMR (282 Hz, C6D6, 20 oC) -145.7 (d, 2F, 3J = 23 Hz, o-Ar),
-159.4 (t, 1F, 3J = 24 Hz, p-Ar), -165.0 (t, 2F, 3J = 23 Hz, mAr); 13C{1H} NMR (125 MHz, C6D6, 20 oC) δ 295.3 (s, 1C,
Mo=C), 157.9, 148.4, 143.0(d, 1JCF = 245 Hz), 139.4(d, 1JCF =
260 Hz), 136.9, 136.8, 136.4, 135.5 (d, 1JCF = 235 Hz), 135.2,
134.7, 131.9, 129.8, 129.1, 127.3, 126.0, 123.4, 109.7, 155.5,
34.4, 32.5, 28.6, 22.7, 21.1, 19.9, 16.8, 14.4. Anal. Calcd for
C46H45F5MoN2O2: C, 66.34; H, 5.45; N, 3.36. Found: C,
66.27; H, 5.49; N, 3.33.
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(DFTO)
(2b).
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 (300 mg, 0.491 mmol) was
dissolved in MeCN (10 mL) and DFTOH (209 mg, 0.491
mmol) was added as solid at room temperature. After 16 h,
the solvent was removed in vacuo to give orange oily product.
Diethyl ether (1 mL) was added and the mixture was stirred
for
30
min
to
give
an
orange
solid
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(DFTO)(MeCN) (356 mg,
75%). The solid was dissolved in toluene and the solvent was
removed in vacuo. This step was repeated 10 times to remove
MeCN and give 2b as a red foam (341 mg). 1H NMR (500
MHz, C6D6, 20 oC) δ 11.64 (br, 1H, Mo=CH), 7.13 (d, 3JHH =
7.5 Hz, 2H), 6.99 (d, 3JHH = 7.5 Hz, 2H), 6.88 (t, 3JHH = 7.5 Hz,
1H), 6.79 (brt, 3JHH = 7 Hz, 2H), 6.60 (brt, 3JHH = 7 Hz, 1H),
5.68 (br, 2H), 2.01 (br, 6H), 1.29 (br, 3H), 1.05 (s, 3H); 19F
NMR (282 MHz, C6D6, 20 oC) δ -140.0 (br, 2F), -140.4 (br,
2F), -148.0 (d, 3JFF = 20 Hz, 2F), -154.7 (br, 2F), -156.5 (t, 3JFF
= 20 Hz, 1F), -162.1 (br, 2F), -162.8 (br, 2F), -163.8 (m, 2F);
13
C{1H} NMR (125 MHz, C6D6, 20 oC) δ 298.8 (br, Mo=C),
165.3, 147.6, 144.6 (dm, 1JCF = 246 Hz), 142.8 (dm, 1JCF = 241
Hz), 141.4 (dm, 1JCF = 246 Hz), 140.5 (dm, 1JCF = 246 Hz),
138.4 (dm, 1JCF = 249 Hz), 137.4 (dm, 1JCF = 251 Hz), 133.9,
133.6, 131.3 (t, 15 Hz), 126.7, 126.4, 122.1, 117.7, 112.3,
110.2, 55.7, 29.1, 15.7 (br); 1H NMR (500 MHz, CDCl3, 20
o
C) δ 11.59 (br, 1H, Mo=CH), 7.37 (d, 3JHH = 7 Hz, 2H), 7.19
(t, 3JHH = 8 Hz, 1H), 7.12 (d, 3JHH = 7.5 Hz, 2H), 7.06 (t, 3JHH =
7.5 Hz, 2H), 6.93 (t, 3JHH = 7.5 Hz, 1H), 5.73 (br, 2H), 2.00
(br, 6H), 1.41 (s, 3H), 1.25 (s, 3H); 19F NMR (282 MHz,
CDCl3, 20 oC) δ -139.4 (br, 2F), -140.1 (br, 2F), -147.2 (d, 3JFF
= 20 Hz, 2F), -154.4 (br, 2F), -155.8 (t, 3JFF = 20 Hz, 1F), 161.9 (br, 2F), -162.5 (br, 2F), -163.3 (m, 2F). The foam-like
solid was recrystallized from a mixture of acetonitrile, diethyl
ether, and pentane to give analytical pure orange crystals of
Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(DFTO)(MeCN)(Et2O)0.5:
1
H NMR (500 MHz, C6D6, 20 oC) δ 12.13(br, 1H, Mo=CH),
7.08 (d, 3JHH = 7.5 Hz, 2H), 7.01 (d, 3JHH = 7.5 Hz, 2H), 6.83
(t, 3JHH = 7.5 Hz, 3H), 6.67(brt, 3JHH = 7 Hz, 1H), 5.83 (br,
2H), 3.25 (q, , 3JHH = 7 Hz, 2H), 2.06 (br, 6H), 1.30 (s, 3H),
1.19 (s, 3H), 1.12 (t, 3JHH = 7 Hz, 3H), 0.62 (br, 3H); 19F NMR
(282 MHz, C6D6, 20 oC) δ -140.3 (br, 4F), -147.9 (d, 3JFF = 20
Hz, 2F), -154.9 (br, 2F), -156.1 (t, 3JFF = 20 Hz, 1F), -162.1
(br, 2F), -162.7 (br, 2F), -163.7 (m, 2F). Anal. Calcd for
C44H31F15MoN3O1.5: C, 52.50; H, 3.10; N, 4.17. Found: C,
52.82; H, 3.29; N, 4.04.
Mo(NAr')(CHCMe2Ph)(Me2Pyr)(DFTO)
(2c).
Mo(NAr')(CHCMe2Ph)(Me2Pyr)2 (130 mg, 0.242 mmol) was
suspended in toluene (5 mL). The suspension was cooled to
-30 oC and DFTOH (103 mg, 0.242 mmol) was added at
-30 oC. The mixture was allowed to warm to room temperature. After 1 hour, the solvent was removed in vacuo to give a
dark red oily product. Pentane (2 mL) was added and the mixture was stirred for 30 min to give a homogenous reddish solution and MeCN (3 drops) was added. The brownish precipitate was recrystallized from a mixture of ether and pentane to
give 2c as a yellow solid; yield 162 mg (76%): 1H NMR (500
MHz, C6D6, 20 oC) δ 12.08 (s, 1H, Mo=CH), 7.13 (d, 3JHH =
7.5 Hz, 2H), 6.99 (d, 3JHH = 7.5 Hz, 2H), 6.91 (d, 3JHH = 7.5
Hz, 2H), 6.88 (d, 3JHH = 7.5 Hz, 1H), 6.82 (d, 3JHH = 7.5 Hz,
1H), 6.61 (d, 3JHH = 7.5 Hz, 1H), 6.53 (d, 3JHH = 7.5 Hz, 2H),
5.85 (br, 2H), 1.93 (br, 6H), 1.69 (br, 6H), 1.30 (s, 3H), 1.24
(s, 3H); 19F NMR (282 MHz, C6D6, 20 oC) δ -139.8 (dm, 3JFF =
23 Hz, 2F), -140.6 (dm, 3JFF = 23 Hz, 2F), -153.9 (t, 3JFF = 23
Hz, 2F), -161.7 (m, 4F); 13C{1H} NMR (125 MHz, C6D6, 20
o
C) δ 294.6 (s, 1C, Mo=C), 164.9, 155.8, 147.2, 144.7 (dm,
1
JCF = 242 Hz), 141.2 (dm, 1JCF = 252 Hz), 138.2(dm, 1JCF =
247 Hz), 133.7 (d, JCF = 22 Hz), 121.8, 117.6, 115.9, 112.5,
109.9 (br), 100.9, 55.2, 30.6, 17.6, 14.2. Crystals of 2c', the
MeCN adduct, were obtained from a mixture of diethyl ether
and MeCN. Anal. Calcd for C42H32F10MoN2O: C, 58.22; H,
3.89; N, 4.64. Found: C, 58.51; H, 4.19; N, 4.26.
Mo(NC6F5)(CH2CH2)(DFTO)2
(3).
Mo(NC6F5)(CHCMe2Ph)(DFTO)2 (138 mg, 0.119 mmol) was
disolved in ether (10 mL). The Schlenk bomb was freezepump-thawed three times. Ethylene (1 atm) was added. After
stirring the mixture at room temperature for 16h, the orange
solution turned dark purple. The solvent was removed and
pentane (1 mL) was added. The mixture was stirred to 30 min
to give purple solid, cooled at -30 oC overnight, and filtered.
The purple solid was washed with cold pentane and dried in
vacuo; yield 105 mg (76%): 1H NMR (500 MHz, tol-d8, 20
o
C) δ 6.95 (d, 3J = 8 Hz, 4H), 6.78 (t, 3J = 8 Hz, 2H), 2.48 (dt, J
= 8 Hz, J = 5 Hz, 2H, CH2=CH2), 1.33 (dt, J = 8 Hz, J = 5 Hz,
2H, CH2=CH2); 19F NMR (282 MHz, tol-d8, 20 oC) δ -140.7
(d, 3JFF = 22 Hz, 8F, o-F), -150.7 (d, 3JFF = 25 Hz, 2F, o-F of
NC6F5), -154.8 (m, 5F), -162.3 (m, 10F); 13C{1H} NMR (125
MHz, tol-d8, 20 oC) δ 161.5, 144.4 (dm, 1JCF = 246 Hz, 8C,
DFTO), 142.9 (dm, 1JCF =253 Hz, 2C, NC6F5), 141.2 (dm, 1JCF
= 255 Hz, 4C, DFTO), 140.5 (dm, 1JCF = 255 Hz, 1C, NC6F5),
138.2 (dm, 1JCF = 253 Hz, 8C, DFTO), 137.3 (dm, 1JCF = 255
Hz, 2C, NC6F5), 133.8(m), 122.5 (m), 118.2, 112.3 (td, 9 Hz, 4
Hz), 61.1 (CH2=CH2); 1H NMR (500 MHz, tol-d8, -80 oC) δ
7.05 (br, 4H), 6.81 (br, 2H), 2.60 (br, 1H), 2.19 (br, 1H), 1.85
(br, 1H), 0.81 (br, 1H); 19F NMR (282 MHz, tol-d8, -80 oC) δ 140.0 (1F), -141.2 (1F), -142.1 (1F), -142.3 (1F), -143.3 (4F),
-151.5 (1F), -152.0 (2F), -154.5 (2F), -154.8 (2F), -159.7 (1F),
-161.4 (1), -162.4 (5F), -163.5 (2F), -164.2 (1F). Anal. Calcd
for C44H10F25MoNO2: C, 45.74; H, 0.87; N, 1.21. Found: C,
45.79; H, 1.06; N, 1.26.
Mo(NC6F5)(CH2CH2)(DCMNBD)(DFTO)2
(5).
Mo(NC6F5)(CH2=CH2)(DFTO)2 (40 mg, 0.0341 mmol) was
disolved in C6D6 (0.5 mL). DCMNBD (7.1 mg, 0.0341 mol)
was added as a solution of C6D6 (0.071 mL, 100 mg/mL).
After 16 hours, reddish-orange crystals were formed (27 mg,
57%). 1H NMR (500 MHz, C6D6, 20 oC) δ 7.16 (d, J = 8 Hz,
2H), 7.10 (br, 2H), 6.89 (br, 2H), 6.79 (br, 1H), 6.72 (t, J = 8
Hz, 1H), 3.91 (s, 1H), 3.85 (s, 1H), 3.73 (s, 3H), 3.07 (td, J =
12 Hz, J = 4 Hz, 1H, CH2=CH2), 2.72 (td, J = 12 Hz, J = 4 Hz,
1H, CH2=CH2), 2.39 (s, 3H, OMe), 2.45 (d, 8 Hz, 1H), 1.94
(d, 8 Hz, 1H), 1.77 (td, J = 12 Hz, J = 4 Hz, 1H, CH 2=CH2),
1.43 (td, J = 12 Hz, J = 4 Hz, 1H, CH2=CH2); 19F NMR (282
MHz, C6D6, 20 oC) δ -133.3 (br, 1F), -137.3 (br, 1F), -140.9 (s,
2F), -145.3 (br, 1F), -150.5 (s, 1F), -151.5 (s, 1F), -152.0 (s,
1F), 154.6 (s, 1F), -156.2 (s, 1F), -157.0 (m, 2F), -158.9 (br,
2F), -162.3 (bs, 4F), -163.9 (m, 4F). Compound 5 slowly
decomposes in the solid state at room temperature and
therefore could not be analyzed.
Observation of Mo(NC6F5)(13CH213CH213CH2)(DFTO)2
(4*).
Mo(NC6F5)(CHCMe2Ph)(DFTO)2 (10 mg) was
dissolved in C6D6 (0.5 mL) in a J. Young NMR tube. The
solution was freeze-pump-thawed three times. 13CH2=13CH2
(<1 atm) was added. After 5 min, all of the starting material
was consumed and 4* was formed in additin to
Mo(NC6F5)(13CH213CH213CH2)(DFTO)2: 1H NMR (500 MHz,
C6D6, 20 oC) δ 3.67 (brd, JCH = 165 Hz, 2H, α-H), 3.55(brd,
JCH = 155 Hz, 2H, α-H), -0.72 (brd, JCH = 154 Hz, 1H, β-H), 1.33(brd, JCH = 154 Hz, 1H, β-H); 13C{1H} NMR (125 MHz,
C6D6, 20 oC) δ 102.5 (Cα), -3.1 (C).
Mo(NC6F5)(13CH213CH213CH213CH2)(DFTO)2 (observation).
Mo(NC6F5)(13CH213CH2)(DFTO)2 (10 mg, 0.00852 mmol) was
disolved in C6D6 (0.5 mL) in a J. Young NMR tube. The solution was freeze-pump-thawed three times. 13CH2=13CH2 was
added through vacuum transfer. After two days, about 1%
Mo(NC6F5)(CH2CH2CH2CH2)(DFTO)2 was formed; 13C{1H}
NMR (125 MHz, C6D6, 20 oC) δ 82.9 (m, AA'BB', Cα), 39.9
(m, AA'BB', C).
Mo(NC6F5)(13CH213CH2-norbornene)(DFTO)2
(observation).
Mo(NC6F5)(13CH213CH2)(DFTO)2 (10 mg,
0.00852 mmol) was dissolved in toulene-d8 (0.5 mL) in a septum-capped tube and cooled at -78 oC. The norbornene (0.8
mg, 0.00852 mmol) was added as a solution of toluene-d8 (0.5
mL) drop by drop. The NMR tube was insert to a -70 oC
NMR. After 1 hour, 69% product was formed: 13C{1H} NMR
(125 MHz, C6D6, 20 oC) δ 84.7 (d, 1Jcc= 37 Hz, MoCα), 46.6
ppm (d, 1Jcc= 37 Hz, Cβ).
Mo(NC6F5)(CHCHCMePh)(DFTO)2 (observation).
Mo(NC6F5)(CH2CH2)(DFTO)2 (10 mg, 0.00853 mmol) was
disolved in toluene (4 mL) and the solution was cooled to
-78 oC. The MPCP (1.11 mg, 0.00853 mmol) was added dropwise as a solution in toluene (1 mL). The purple color
changed to orange immediately. After one hour, the mixture
was warmed up to room temperature and the solvent removed
to give an oily orange product (12 mg): 1H NMR (500 MHz,
C6D6, 20 oC) δ 12.10 (dd, 1JCH = 130 Hz, 3JHH = 9 Hz, MoCH),
8.33 (dd, 1JCH = 159 Hz, 3JHH = 9 Hz, β-H). The other resonances overlap with polymer resonances; 13C{1H} NMR (125
MHz, C6D6, 20 oC) δ 264.5 (s, Cα), 136.0 (s, Cβ).
Procedure for ROMP of DCMNBD. The initiator (1 mg)
was dissolved in CDCl3 (0.5 mL). DCMNBD (100 eq) was
added as a solution in CDCl3 (0.5 mL). After 30 min, benzal-
dehyde (0.1 mL) was added to the mixture. The reaction
mixture became deep green within 5 minutes, and was stirred
for 1 h. The entire mixture was added dropwise to 100 mL of
vigorously stirred methanol. A fine white solid formed immediately. After 2 h the polymer was filtered off, rinsed with
MeOH, and dried in vacuo.
Measurement of conversion of DCMNBD by 3. DCMNBD
(50 mg, 0.240 mmol) and an internal standard of anthracene
were dissolved in CDCl3 in a J.Young NMR tube. A 1H NMR
spectrum was obtained. A 12.0 mM solution of 3 was prepared
and 0.2 mL (2.4 μmol) was added to the NMR tube. The tube
was inverted to mix, and the tube was then heated to 50 °C. 1H
NMR spectra were obtained over 120 h. Conversion was
measured by integration of the olefinic resonance of
DCMNBD against the anthracene internal standard.
ASSOCIATED CONTENT
Supporting Information. Figures S1, S2, and S3. Crystallographic details and data for 2b', 3, and 5. This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: rrs@mit.edu
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
R.R.S. thanks the National Science Foundation (CHE-1111133)
and the Department of Energy (DE-FG02-86ER13564) for supporting this research. The Department of Chemistry thanks the
NSF (CHE-9808061) for funds to purchase a 500 MHz NMR
instrument and an X-ray diffractometer (CHE-0946721).
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Scheme 1. A mechanism that leads to cis,isotactic-poly(DCMNBD).
11
Table of Contents
C 6F 5
C6F5
N
O
C 6F 5
C 6F 5
CO2Me
CMe2Ph
Mo
O
C 6F 5
cis,isotactic
polyDCMNBD
CO2Me
12
Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum
Imido Alkylidene and Ethylene Complexes
by
Jian Yuan, Richard Schrock*, Laura C. H. Gerber, Peter Müller, and Stacey Smith
Figure S1. Molecular weight (Mn) of poly(DCMNBD) (in CHCl3 vs. polystyrene)
versus equiv of monomer (n) added.
Figure S2. Molecular weight (Mn) of poly(DCMNBD) (in CHCl3 versus polystyrene)
versus equivalents of monomer (n) added using 2b as a catalyst.
Figure S3. The 2D 13C-1H HMBC spectrum of 8 in CDCl3.
Crystallographic details. Low-temperature diffraction data (-and -scans) were collected on a
Siemens Platform three-circle diffractometer coupled to a Bruker-AXS Smart Apex CCD
detector with graphite-monochromated Mo K radiation ( = 0.71073 Å) for the structure of
compound 5 and on a Bruker-AXS X8 Kappa Duo diffractometer coupled to a Smart Apex2
CCD detector with Mo K radiation ( = 0.71073 Å) from an Incoatec IμS micro-source for the
structures of compounds 2b' and 3. The structures were solved by direct methods using
SHELXS1 and refined against F2 on all data by full-matrix least squares with SHELXL-972
following established refinement strategies.3
All non-hydrogen atoms were refined
anisotropically. Except for hydrogen atoms on carbon atoms in direct contact with the metal (for
details see below), all hydrogen atoms were included into the model at geometrically calculated
positions and refined using a riding model. The isotropic displacement parameters of all
hydrogen atoms were fixed to 1.2 times the U value of the atoms they are linked to (1.5 times for
methyl groups).
Compound 2b' crystallizes in the monoclinic space group P21/c with two molecules of
2b' and one disordered molecule of diethyl ether per asymmetric unit. One of the two
independent molecules, that of molybdenum atom Mo1, is well-behaved, the other shows higher
than average molecular motion of some of the ligands. This motion could be modeled as
disorder over two components for the pentafluorophenyl and the alkylidene ligands. For
discussions of molecular geometry throughout this manuscript, paremeters derived from the
well-behaved molecule are used. All disorders were refined with the help of similarity restraints
on 1-2 and 1-3 distances and displacement parameters as well as rigid bond restraints for
anisotropic displacement parameters. The ratios between the two components of all disorders
were refined freely and converged at 0.53(4) (alkylidene), 0.53(2) (pentafluorophenyl), and
0.550(5) (solvent), respectively. Coordinates for the hydrogen atoms on C1, C51 and C51A, that
is the carbon atoms directly binding to the metal, were taken from the difference Fourier
synthesis where they were found among the eight highest residual density maxima (the same
starting-coordinates were used for the hydrogen atoms in C51 and C51A). These three hydrogen
atom positions were subsequently refined semi-freely with the help of distance restraints (target
C—H-distance 0.95(2) Å). The circumstance that the crystal contains one solvent molecule for
every two target molecules leads to a non-integer value for the element type oxygen in the
empirical formula.
Compound 3 crystallizes in the monoclinic space group P21/c with one molecule per
asymmetric unit. Coordinates for the hydrogen atoms on C1 and C2, that is the carbon atoms
directly binding to the metal, were taken from the difference Fourier synthesis where they
corresponded to the four highest residual density maxima. These hydrogen atoms were
subsequently refined semi-freely with the help of distance restraints on the C—H-distances
(target 0.95(2) Å) and similarity restraints on the two H—C—H-angles.
Compound 5 crystallizes in the triclinic space group P1̄ with one molecule of 5 and two
benzene molecules per asymmetric unit. One of the two benzene molecules is disordered over
two positions. The ratio between the two components of this disorders was refined freely and
converged at 0.710(8). Similarity restraints on 1-2 and 1-3 distances and displacement
parameters as well as rigid bond restraints for anisotropic displacement parameters were applied
to all atoms in the solvent molecules. In addition, the three benzene molecules were restraint to
be approximately planar. Coordinates for the hydrogen atoms on C1 and C2, that is the carbon
atoms directly binding to the metal, were taken from the difference Fourier synthesis where they
corresponded to the four highest residual density maxima. These hydrogen atoms were
subsequently refined semi-freely with the help of distance restraints on the C—H-distances
(target 0.95(2) Å) and similarity restraints on the two H—C—H-angles.
Details of the data quality, a summary of the residual values of the refinements as well as
all other pertinent parameters are listed in Tables S1-S15.
Acknowledgements
The diffractometer used for data collections of compounds 2b' and 3 was purchased with
the help of funding from the National Science Foundation (NSF) under Grant Number CHE0946721.
Table S1. Crystal data and structure refinement for 2b'.
Identification code
X8_12207
Empirical formula
C44 H31 F15 Mo N3 O1.5
Formula weight
1006.66
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P1̄
Unit cell dimensions
a = 11.9807(8) Å
= 96.2670(10)°
b = 16.7624(11) Å
= 105.5080(10)°
c = 22.1895(15) Å
 = 100.9520(10)°
Volume
4155.1(5) Å3
Z
4
Density (calculated)
1.609 Mg/m3
Absorption coefficient
0.424 mm-1
F(000)
2020
Crystal size
0.32 x 0.17 x 0.14 mm3
Theta range for data collection
1.26 to 31.51°.
Index ranges
-16<=h<=17, -24<=k<=24, -32<=l<=32
Reflections collected
249296
Independent reflections
27615 [Rint = 0.0325]
Completeness to theta = 31.51°
99.8 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9430 and 0.8762
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
27615 / 870 / 1420
Goodness-of-fit on F2
1.023
Final R indices [I>2σ(I)]
R1 = 0.0270, wR2 = 0.0657
R indices (all data)
R1 = 0.0332, wR2 = 0.0693
Largest diff. peak and hole
0.552 and -0.490 e.Å-3
Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for 2b'. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
Mo(1)
6310(1)
8209(1)
2724(1)
15(1)
C(1)
7004(1)
7750(1)
2140(1)
20(1)
C(2)
6664(1)
7390(1)
1436(1)
21(1)
C(3)
7802(1)
7361(1)
1244(1)
31(1)
C(4)
5947(1)
6501(1)
1360(1)
29(1)
C(5)
5954(1)
7911(1)
1033(1)
20(1)
C(6)
6411(1)
8763(1)
1120(1)
24(1)
C(7)
5771(1)
9266(1)
789(1)
27(1)
C(8)
4667(1)
8927(1)
347(1)
28(1)
C(9)
4220(1)
8082(1)
236(1)
27(1)
C(10)
4858(1)
7579(1)
578(1)
24(1)
N(1)
4939(1)
8205(1)
2187(1)
18(1)
C(11)
3930(1)
8384(1)
1811(1)
18(1)
C(12)
3788(1)
9190(1)
1785(1)
23(1)
F(12)
4637(1)
9824(1)
2154(1)
35(1)
C(13)
2785(1)
9353(1)
1388(1)
24(1)
F(13)
2671(1)
10130(1)
1377(1)
37(1)
C(14)
1880(1)
8714(1)
1009(1)
24(1)
F(14)
910(1)
8878(1)
636(1)
33(1)
C(15)
1973(1)
7910(1)
1039(1)
24(1)
F(15)
1073(1)
7287(1)
703(1)
36(1)
C(16)
2989(1)
7753(1)
1428(1)
21(1)
F(16)
3068(1)
6969(1)
1439(1)
30(1)
N(3)
6956(1)
9489(1)
2630(1)
22(1)
C(17)
7368(1)
10164(1)
2667(1)
29(1)
C(18)
7914(2)
11033(1)
2720(1)
58(1)
N(2)
5790(1)
7218(1)
3156(1)
19(1)
C(21)
3774(1)
7495(1)
3159(1)
31(1)
C(22)
4794(1)
7102(1)
3379(1)
24(1)
C(23)
4886(1)
6538(1)
3785(1)
32(1)
C(24)
5964(1)
6291(1)
3822(1)
31(1)
C(25)
6502(1)
6711(1)
3438(1)
22(1)
C(26)
7664(1)
6666(1)
3328(1)
29(1)
O(1)
7643(1)
8618(1)
3525(1)
18(1)
C(31)
8342(1)
9335(1)
3859(1)
17(1)
C(32)
7916(1)
9859(1)
4235(1)
19(1)
C(33)
8647(1)
10615(1)
4568(1)
24(1)
C(34)
9797(1)
10860(1)
4533(1)
26(1)
C(35)
10221(1)
10346(1)
4160(1)
25(1)
C(36)
9507(1)
9588(1)
3823(1)
20(1)
C(37)
9949(1)
9048(1)
3408(1)
22(1)
C(38)
10036(1)
9229(1)
2823(1)
26(1)
F(38)
9720(1)
9904(1)
2625(1)
32(1)
C(39)
10418(1)
8724(1)
2423(1)
30(1)
F(39)
10471(1)
8921(1)
1860(1)
42(1)
C(40)
10721(1)
8014(1)
2601(1)
31(1)
F(40)
11073(1)
7518(1)
2210(1)
42(1)
C(41)
10656(1)
7814(1)
3180(1)
28(1)
F(41)
10955(1)
7131(1)
3359(1)
35(1)
C(42)
10275(1)
8333(1)
3573(1)
24(1)
F(42)
10226(1)
8122(1)
4132(1)
28(1)
C(43)
C(44)
F(44)
C(45)
F(45)
C(46)
F(46)
C(47)
F(47)
C(48)
F(48)
Mo(2)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
C(58)
C(59)
C(60)
C(51A)
C(52A)
C(53A)
C(54A)
C(55A)
C(56A)
C(57A)
C(58A)
C(59A)
C(60A)
N(4)
C(61)
C(62)
F(62)
C(63)
F(63)
C(64)
F(64)
C(65)
F(65)
C(66)
F(66)
C(61A)
C(62A)
F(62A)
C(63A)
F(63A)
C(64A)
F(64A)
C(65A)
F(65A)
C(66A)
F(66A)
N(6)
6676(1)
5820(1)
6099(1)
4677(1)
3875(1)
4353(1)
3242(1)
5178(1)
4865(1)
6317(1)
7104(1)
8753(1)
7616(9)
6916(8)
5806(8)
7781(14)
6512(12)
5856(10)
5473(16)
5680(20)
6285(13)
6700(20)
7623(12)
6984(9)
5883(9)
7862(15)
6568(13)
5920(14)
5519(19)
5770(20)
6387(14)
6790(20)
8826(1)
8834(5)
8574(9)
8356(10)
8526(10)
8234(10)
8774(11)
8744(9)
9068(16)
9327(14)
9112(16)
9429(13)
8769(5)
8361(9)
8072(11)
8269(10)
7874(11)
8602(10)
8496(8)
9036(17)
9317(17)
9121(15)
9531(13)
7399(1)
9610(1)
10038(1)
10677(1)
9832(1)
10262(1)
9180(1)
8974(1)
8740(1)
8122(1)
8955(1)
8526(1)
7044(1)
7709(6)
8024(5)
8260(6)
8805(8)
7373(6)
6591(5)
5983(7)
6148(8)
6921(7)
7537(8)
7678(8)
8014(6)
8263(6)
8796(9)
7377(6)
6586(7)
5984(8)
6158(9)
6938(7)
7529(9)
6776(1)
6344(5)
5495(5)
5052(5)
5087(5)
4269(4)
5522(6)
5142(7)
6363(6)
6798(8)
6761(6)
7590(6)
6406(5)
5550(5)
5068(4)
5182(4)
4361(4)
5670(5)
5302(5)
6510(5)
6970(6)
6873(6)
7685(5)
5900(1)
4266(1)
4022(1)
3733(1)
4069(1)
3834(1)
4358(1)
4403(1)
4609(1)
4904(1)
4557(1)
4812(1)
7957(1)
7813(5)
7247(5)
7371(6)
7187(8)
6646(5)
6652(5)
6118(6)
5559(7)
5538(5)
6078(6)
7721(7)
7156(6)
7284(7)
7116(10)
6551(6)
6558(7)
6021(7)
5473(7)
5451(6)
5994(7)
7187(1)
6613(3)
6475(4)
6906(4)
5888(4)
5761(4)
5440(4)
4870(4)
5558(4)
5127(5)
6144(5)
6264(6)
6602(4)
6402(4)
6811(5)
5798(4)
5623(5)
5378(4)
4790(4)
5571(5)
5150(6)
6171(4)
6341(6)
7803(1)
20(1)
28(1)
41(1)
34(1)
57(1)
31(1)
44(1)
26(1)
39(1)
22(1)
30(1)
14(1)
12(1)
18(1)
32(2)
29(2)
20(1)
20(1)
31(2)
36(2)
34(2)
26(1)
22(2)
22(1)
33(2)
28(2)
21(1)
29(2)
31(2)
31(2)
29(2)
27(2)
20(1)
26(1)
39(2)
56(2)
52(2)
86(2)
53(2)
85(2)
45(2)
63(2)
36(2)
42(2)
22(1)
30(1)
45(2)
39(2)
68(2)
37(2)
56(2)
33(1)
51(2)
21(1)
29(1)
21(1)
C(67)
6737(1)
5308(1)
7785(1)
23(1)
C(68)
5884(2)
4560(1)
7771(1)
36(1)
N(5)
10337(1)
7925(1)
8334(1)
17(1)
C(71)
11490(1)
7057(1)
7850(1)
23(1)
C(72)
11416(1)
7742(1)
8317(1)
19(1)
C(73)
12330(1)
8320(1)
8746(1)
31(1)
C(74)
11810(1)
8884(1)
9044(1)
29(1)
C(75)
10603(1)
8629(1)
8787(1)
20(1)
C(76)
9691(1)
9020(1)
8962(1)
28(1)
O(2)
8954(1)
6829(1)
8847(1)
19(1)
C(81)
8520(1)
6221(1)
9120(1)
20(1)
C(82)
8982(1)
5509(1)
9154(1)
22(1)
C(83)
8455(1)
4856(1)
9403(1)
28(1)
C(84)
7484(1)
4900(1)
9619(1)
31(1)
C(85)
7032(1)
5603(1)
9595(1)
29(1)
C(86)
7544(1)
6264(1)
9351(1)
24(1)
C(87)
7022(1)
6997(1)
9292(1)
25(1)
C(88)
5912(1)
6951(1)
8869(1)
29(1)
F(88)
5290(1)
6229(1)
8497(1)
38(1)
C(89)
5427(1)
7626(1)
8797(1)
34(1)
F(89)
4375(1)
7554(1)
8363(1)
50(1)
C(90)
6038(1)
8383(1)
9163(1)
34(1)
F(90)
5560(1)
9039(1)
9093(1)
47(1)
C(91)
7137(1)
8457(1)
9589(1)
32(1)
F(91)
7740(1)
9190(1)
9937(1)
42(1)
C(92)
7617(1)
7772(1)
9646(1)
27(1)
F(92)
8692(1)
7860(1)
10057(1)
35(1)
C(93)
9982(1)
5428(1)
8894(1)
22(1)
C(94)
9860(1)
4792(1)
8404(1)
26(1)
F(94)
8798(1)
4266(1)
8136(1)
34(1)
C(95)
10796(1)
4678(1)
8178(1)
30(1)
F(95)
10646(1)
4060(1)
7706(1)
42(1)
C(96)
11899(1)
5205(1)
8441(1)
28(1)
F(96)
12815(1)
5106(1)
8226(1)
37(1)
C(97)
12054(1)
5845(1)
8925(1)
26(1)
F(97)
13132(1)
6349(1)
9186(1)
33(1)
C(98)
11106(1)
5954(1)
9140(1)
23(1)
F(98)
11303(1)
6567(1)
9621(1)
29(1)
C(1S)
1506(12)
5384(8)
6682(8)
56(2)
C(2S)
2466(7)
5951(4)
6530(3)
57(2)
O(1S)
1931(3)
6433(2)
6099(2)
47(1)
C(3S)
2765(3)
6909(3)
5860(2)
58(1)
C(4S)
2152(5)
7374(3)
5391(3)
62(1)
C(1SA)
1865(15)
5508(9)
6685(10)
57(3)
C(2SA)
2562(8)
6266(4)
6530(4)
46(2)
O(1SA)
1775(3)
6745(2)
6258(2)
36(1)
C(3SA)
2344(4)
7456(2)
6077(2)
38(1)
C(4SA)
2693(7)
7283(4)
5484(3)
59(2)
________________________________________________________________________________
Table S3. Bond lengths [Å] and angles [°] for 2b'
_____________________________________________________
Mo(1)-N(1)
1.7512(10)
Mo(1)-C(1)
1.8887(12)
Mo(1)-O(1)
1.9947(8)
Mo(1)-N(2)
2.0836(10)
Mo(1)-N(3)
2.1904(11)
C(1)-C(2)
1.5260(17)
C(1)-H(1)
0.950(13)
C(2)-C(5)
1.5280(18)
C(2)-C(4)
1.5393(18)
C(2)-C(3)
1.5402(19)
C(3)-H(3A)
0.9800
C(3)-H(3B)
0.9800
C(3)-H(3C)
0.9800
C(4)-H(4A)
0.9800
C(4)-H(4B)
0.9800
C(4)-H(4C)
0.9800
C(5)-C(10)
1.3949(17)
C(5)-C(6)
1.3996(17)
C(6)-C(7)
1.3855(19)
C(6)-H(6)
0.9500
C(7)-C(8)
1.390(2)
C(7)-H(7)
0.9500
C(8)-C(9)
1.384(2)
C(8)-H(8)
0.9500
C(9)-C(10)
1.3942(19)
C(9)-H(9)
0.9500
C(10)-H(10)
0.9500
N(1)-C(11)
1.3780(15)
C(11)-C(16)
1.3975(16)
C(11)-C(12)
1.3989(17)
C(12)-F(12)
1.3376(14)
C(12)-C(13)
1.3803(18)
C(13)-F(13)
1.3374(15)
C(13)-C(14)
1.3797(19)
C(14)-F(14)
1.3290(15)
C(14)-C(15)
1.3800(19)
C(15)-F(15)
1.3340(15)
C(15)-C(16)
1.3811(18)
C(16)-F(16)
1.3372(15)
N(3)-C(17)
1.1310(17)
C(17)-C(18)
1.456(2)
C(18)-H(18A)
0.9800
C(18)-H(18B)
0.9800
C(18)-H(18C)
0.9800
N(2)-C(25)
1.3949(16)
N(2)-C(22)
1.3977(16)
C(21)-C(22)
1.492(2)
C(21)-H(21A)
0.9800
C(21)-H(21B)
0.9800
C(21)-H(21C)
0.9800
C(22)-C(23)
1.3741(19)
C(23)-C(24)
1.415(2)
C(23)-H(23)
0.9500
C(24)-C(25)
1.3753(19)
C(24)-H(24)
C(25)-C(26)
C(26)-H(26A)
C(26)-H(26B)
C(26)-H(26C)
O(1)-C(31)
C(31)-C(32)
C(31)-C(36)
C(32)-C(33)
C(32)-C(43)
C(33)-C(34)
C(33)-H(33)
C(34)-C(35)
C(34)-H(34)
C(35)-C(36)
C(35)-H(35)
C(36)-C(37)
C(37)-C(42)
C(37)-C(38)
C(38)-F(38)
C(38)-C(39)
C(39)-F(39)
C(39)-C(40)
C(40)-F(40)
C(40)-C(41)
C(41)-F(41)
C(41)-C(42)
C(42)-F(42)
C(43)-C(44)
C(43)-C(48)
C(44)-F(44)
C(44)-C(45)
C(45)-F(45)
C(45)-C(46)
C(46)-F(46)
C(46)-C(47)
C(47)-F(47)
C(47)-C(48)
C(48)-F(48)
Mo(2)-N(4)
Mo(2)-C(51A)
Mo(2)-C(51)
Mo(2)-O(2)
Mo(2)-N(5)
Mo(2)-N(6)
C(51)-C(52)
C(51)-H(51)
C(51)-H(51A)
C(52)-C(55)
C(52)-C(53)
C(52)-C(54)
C(53)-H(53A)
C(53)-H(53B)
C(53)-H(53C)
C(54)-H(54A)
C(54)-H(54B)
0.9500
1.489(2)
0.9800
0.9800
0.9800
1.3362(13)
1.4028(17)
1.4060(17)
1.3953(16)
1.4862(18)
1.386(2)
0.9500
1.386(2)
0.9500
1.3941(16)
0.9500
1.4861(18)
1.3859(19)
1.3894(18)
1.3422(17)
1.384(2)
1.3406(16)
1.376(2)
1.3389(16)
1.383(2)
1.3331(17)
1.3860(19)
1.3391(15)
1.3889(17)
1.3890(17)
1.3422(16)
1.382(2)
1.3386(16)
1.372(2)
1.3429(17)
1.379(2)
1.3305(16)
1.3830(18)
1.3372(14)
1.7486(10)
1.878(8)
1.904(6)
2.0049(8)
2.0740(10)
2.1922(10)
1.518(7)
0.961(17)
0.74(3)
1.529(7)
1.540(8)
1.550(8)
0.9800
0.9800
0.9800
0.9800
0.9800
C(54)-H(54C)
C(55)-C(60)
C(55)-C(56)
C(56)-C(57)
C(56)-H(56)
C(57)-C(58)
C(57)-H(57)
C(58)-C(59)
C(58)-H(58)
C(59)-C(60)
C(59)-H(59)
C(60)-H(60)
C(51A)-C(52A)
C(51A)-H(51)
C(51A)-H(51A)
C(52A)-C(55A)
C(52A)-C(53A)
C(52A)-C(54A)
C(53A)-H(53D)
C(53A)-H(53E)
C(53A)-H(53F)
C(54A)-H(54D)
C(54A)-H(54E)
C(54A)-H(54F)
C(55A)-C(60A)
C(55A)-C(56A)
C(56A)-C(57A)
C(56A)-H(56A)
C(57A)-C(58A)
C(57A)-H(57A)
C(58A)-C(59A)
C(58A)-H(58A)
C(59A)-C(60A)
C(59A)-H(59A)
C(60A)-H(60A)
N(4)-C(61A)
N(4)-C(61)
C(61)-C(62)
C(61)-C(66)
C(62)-F(62)
C(62)-C(63)
C(63)-F(63)
C(63)-C(64)
C(64)-F(64)
C(64)-C(65)
C(65)-F(65)
C(65)-C(66)
C(66)-F(66)
C(61A)-C(66A)
C(61A)-C(62A)
C(62A)-F(62A)
C(62A)-C(63A)
C(63A)-F(63A)
C(63A)-C(64A)
C(64A)-F(64A)
C(64A)-C(65A)
0.9800
1.386(7)
1.398(8)
1.385(8)
0.9500
1.375(8)
0.9500
1.374(9)
0.9500
1.401(8)
0.9500
0.9500
1.510(9)
1.16(3)
0.951(19)
1.522(8)
1.542(9)
1.543(9)
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.374(8)
1.408(9)
1.385(9)
0.9500
1.376(8)
0.9500
1.387(9)
0.9500
1.383(9)
0.9500
0.9500
1.354(8)
1.398(6)
1.379(8)
1.393(8)
1.323(8)
1.383(8)
1.328(8)
1.359(8)
1.340(8)
1.364(8)
1.330(8)
1.379(8)
1.345(8)
1.401(8)
1.405(8)
1.349(7)
1.381(8)
1.344(7)
1.392(7)
1.343(7)
1.380(7)
C(65A)-F(65A)
C(65A)-C(66A)
C(66A)-F(66A)
N(6)-C(67)
C(67)-C(68)
C(68)-H(68A)
C(68)-H(68B)
C(68)-H(68C)
N(5)-C(75)
N(5)-C(72)
C(71)-C(72)
C(71)-H(71A)
C(71)-H(71B)
C(71)-H(71C)
C(72)-C(73)
C(73)-C(74)
C(73)-H(73)
C(74)-C(75)
C(74)-H(74)
C(75)-C(76)
C(76)-H(76A)
C(76)-H(76B)
C(76)-H(76C)
O(2)-C(81)
C(81)-C(86)
C(81)-C(82)
C(82)-C(83)
C(82)-C(93)
C(83)-C(84)
C(83)-H(83)
C(84)-C(85)
C(84)-H(84)
C(85)-C(86)
C(85)-H(85)
C(86)-C(87)
C(87)-C(88)
C(87)-C(92)
C(88)-F(88)
C(88)-C(89)
C(89)-F(89)
C(89)-C(90)
C(90)-F(90)
C(90)-C(91)
C(91)-F(91)
C(91)-C(92)
C(92)-F(92)
C(93)-C(98)
C(93)-C(94)
C(94)-F(94)
C(94)-C(95)
C(95)-F(95)
C(95)-C(96)
C(96)-F(96)
C(96)-C(97)
C(97)-F(97)
C(97)-C(98)
1.344(8)
1.371(8)
1.331(8)
1.1354(16)
1.4513(18)
0.9800
0.9800
0.9800
1.3887(15)
1.3926(15)
1.4936(17)
0.9800
0.9800
0.9800
1.3713(18)
1.4239(19)
0.9500
1.3668(17)
0.9500
1.4897(17)
0.9800
0.9800
0.9800
1.3328(14)
1.4064(18)
1.4105(18)
1.3986(17)
1.4827(19)
1.383(2)
0.9500
1.388(2)
0.9500
1.3954(18)
0.9500
1.484(2)
1.390(2)
1.3920(18)
1.3456(16)
1.372(2)
1.3412(19)
1.382(2)
1.3381(18)
1.375(2)
1.3360(16)
1.381(2)
1.3349(17)
1.3931(18)
1.3949(18)
1.3432(16)
1.380(2)
1.3403(16)
1.378(2)
1.3380(17)
1.3809(19)
1.3397(16)
1.379(2)
C(98)-F(98)
C(1S)-C(2S)
C(1S)-H(1S1)
C(1S)-H(1S2)
C(1S)-H(1S3)
C(2S)-O(1S)
C(2S)-H(2S1)
C(2S)-H(2S2)
O(1S)-C(3S)
C(3S)-C(4S)
C(3S)-H(3S1)
C(3S)-H(3S2)
C(4S)-H(4S1)
C(4S)-H(4S2)
C(4S)-H(4S3)
C(1SA)-C(2SA)
C(1SA)-H(1S4)
C(1SA)-H(1S5)
C(1SA)-H(1S6)
C(2SA)-O(1SA)
C(2SA)-H(2S3)
C(2SA)-H(2S4)
O(1SA)-C(3SA)
C(3SA)-C(4SA)
C(3SA)-H(3S3)
C(3SA)-H(3S4)
C(4SA)-H(4S4)
C(4SA)-H(4S5)
C(4SA)-H(4S6)
N(1)-Mo(1)-C(1)
N(1)-Mo(1)-O(1)
C(1)-Mo(1)-O(1)
N(1)-Mo(1)-N(2)
C(1)-Mo(1)-N(2)
O(1)-Mo(1)-N(2)
N(1)-Mo(1)-N(3)
C(1)-Mo(1)-N(3)
O(1)-Mo(1)-N(3)
N(2)-Mo(1)-N(3)
C(2)-C(1)-Mo(1)
C(2)-C(1)-H(1)
Mo(1)-C(1)-H(1)
C(1)-C(2)-C(5)
C(1)-C(2)-C(4)
C(5)-C(2)-C(4)
C(1)-C(2)-C(3)
C(5)-C(2)-C(3)
C(4)-C(2)-C(3)
C(2)-C(3)-H(3A)
C(2)-C(3)-H(3B)
H(3A)-C(3)-H(3B)
C(2)-C(3)-H(3C)
H(3A)-C(3)-H(3C)
H(3B)-C(3)-H(3C)
C(2)-C(4)-H(4A)
1.3356(14)
1.484(9)
0.9800
0.9800
0.9800
1.420(6)
0.9900
0.9900
1.410(5)
1.490(6)
0.9900
0.9900
0.9800
0.9800
0.9800
1.508(9)
0.9800
0.9800
0.9800
1.409(7)
0.9900
0.9900
1.410(4)
1.499(6)
0.9900
0.9900
0.9800
0.9800
0.9800
98.05(5)
154.35(4)
104.97(5)
99.78(4)
103.16(5)
85.98(4)
88.99(4)
95.04(5)
78.01(4)
158.37(4)
139.00(9)
114.5(10)
106.4(10)
110.65(10)
106.19(10)
112.31(11)
109.31(11)
109.64(11)
108.63(11)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C(2)-C(4)-H(4B)
H(4A)-C(4)-H(4B)
C(2)-C(4)-H(4C)
H(4A)-C(4)-H(4C)
H(4B)-C(4)-H(4C)
C(10)-C(5)-C(6)
C(10)-C(5)-C(2)
C(6)-C(5)-C(2)
C(7)-C(6)-C(5)
C(7)-C(6)-H(6)
C(5)-C(6)-H(6)
C(6)-C(7)-C(8)
C(6)-C(7)-H(7)
C(8)-C(7)-H(7)
C(9)-C(8)-C(7)
C(9)-C(8)-H(8)
C(7)-C(8)-H(8)
C(8)-C(9)-C(10)
C(8)-C(9)-H(9)
C(10)-C(9)-H(9)
C(9)-C(10)-C(5)
C(9)-C(10)-H(10)
C(5)-C(10)-H(10)
C(11)-N(1)-Mo(1)
N(1)-C(11)-C(16)
N(1)-C(11)-C(12)
C(16)-C(11)-C(12)
F(12)-C(12)-C(13)
F(12)-C(12)-C(11)
C(13)-C(12)-C(11)
F(13)-C(13)-C(14)
F(13)-C(13)-C(12)
C(14)-C(13)-C(12)
F(14)-C(14)-C(13)
F(14)-C(14)-C(15)
C(13)-C(14)-C(15)
F(15)-C(15)-C(14)
F(15)-C(15)-C(16)
C(14)-C(15)-C(16)
F(16)-C(16)-C(15)
F(16)-C(16)-C(11)
C(15)-C(16)-C(11)
C(17)-N(3)-Mo(1)
N(3)-C(17)-C(18)
C(17)-C(18)-H(18A)
C(17)-C(18)-H(18B)
H(18A)-C(18)-H(18B)
C(17)-C(18)-H(18C)
H(18A)-C(18)-H(18C)
H(18B)-C(18)-H(18C)
C(25)-N(2)-C(22)
C(25)-N(2)-Mo(1)
C(22)-N(2)-Mo(1)
C(22)-C(21)-H(21A)
C(22)-C(21)-H(21B)
H(21A)-C(21)-H(21B)
109.5
109.5
109.5
109.5
109.5
117.81(12)
122.98(11)
119.21(11)
121.18(12)
119.4
119.4
120.22(13)
119.9
119.9
119.47(13)
120.3
120.3
120.17(12)
119.9
119.9
121.07(12)
119.5
119.5
167.56(9)
120.62(11)
122.92(11)
116.46(11)
118.57(11)
119.73(11)
121.71(12)
119.42(12)
120.32(12)
120.24(12)
119.72(12)
120.64(12)
119.60(12)
120.10(12)
120.09(12)
119.79(12)
118.68(11)
119.18(11)
122.14(12)
170.69(11)
179.21(19)
109.5
109.5
109.5
109.5
109.5
109.5
106.65(10)
126.63(8)
124.30(9)
109.5
109.5
109.5
C(22)-C(21)-H(21C)
H(21A)-C(21)-H(21C)
H(21B)-C(21)-H(21C)
C(23)-C(22)-N(2)
C(23)-C(22)-C(21)
N(2)-C(22)-C(21)
C(22)-C(23)-C(24)
C(22)-C(23)-H(23)
C(24)-C(23)-H(23)
C(25)-C(24)-C(23)
C(25)-C(24)-H(24)
C(23)-C(24)-H(24)
C(24)-C(25)-N(2)
C(24)-C(25)-C(26)
N(2)-C(25)-C(26)
C(25)-C(26)-H(26A)
C(25)-C(26)-H(26B)
H(26A)-C(26)-H(26B)
C(25)-C(26)-H(26C)
H(26A)-C(26)-H(26C)
H(26B)-C(26)-H(26C)
C(31)-O(1)-Mo(1)
O(1)-C(31)-C(32)
O(1)-C(31)-C(36)
C(32)-C(31)-C(36)
C(33)-C(32)-C(31)
C(33)-C(32)-C(43)
C(31)-C(32)-C(43)
C(34)-C(33)-C(32)
C(34)-C(33)-H(33)
C(32)-C(33)-H(33)
C(35)-C(34)-C(33)
C(35)-C(34)-H(34)
C(33)-C(34)-H(34)
C(34)-C(35)-C(36)
C(34)-C(35)-H(35)
C(36)-C(35)-H(35)
C(35)-C(36)-C(31)
C(35)-C(36)-C(37)
C(31)-C(36)-C(37)
C(42)-C(37)-C(38)
C(42)-C(37)-C(36)
C(38)-C(37)-C(36)
F(38)-C(38)-C(39)
F(38)-C(38)-C(37)
C(39)-C(38)-C(37)
F(39)-C(39)-C(40)
F(39)-C(39)-C(38)
C(40)-C(39)-C(38)
F(40)-C(40)-C(39)
F(40)-C(40)-C(41)
C(39)-C(40)-C(41)
F(41)-C(41)-C(40)
F(41)-C(41)-C(42)
C(40)-C(41)-C(42)
F(42)-C(42)-C(37)
109.5
109.5
109.5
109.24(13)
127.05(13)
123.57(11)
107.41(12)
126.3
126.3
107.49(12)
126.3
126.3
109.21(12)
127.41(13)
123.37(11)
109.5
109.5
109.5
109.5
109.5
109.5
138.72(7)
120.76(11)
120.35(11)
118.86(10)
120.01(12)
120.47(11)
119.51(10)
120.88(12)
119.6
119.6
119.38(11)
120.3
120.3
120.76(12)
119.6
119.6
120.12(12)
120.75(11)
119.11(10)
116.29(12)
122.32(11)
121.39(12)
117.79(12)
119.91(12)
122.28(13)
120.37(13)
119.92(14)
119.70(13)
119.83(14)
120.26(14)
119.91(13)
120.41(13)
120.47(13)
119.12(14)
119.74(11)
F(42)-C(42)-C(41)
C(37)-C(42)-C(41)
C(44)-C(43)-C(48)
C(44)-C(43)-C(32)
C(48)-C(43)-C(32)
F(44)-C(44)-C(45)
F(44)-C(44)-C(43)
C(45)-C(44)-C(43)
F(45)-C(45)-C(46)
F(45)-C(45)-C(44)
C(46)-C(45)-C(44)
F(46)-C(46)-C(45)
F(46)-C(46)-C(47)
C(45)-C(46)-C(47)
F(47)-C(47)-C(46)
F(47)-C(47)-C(48)
C(46)-C(47)-C(48)
F(48)-C(48)-C(47)
F(48)-C(48)-C(43)
C(47)-C(48)-C(43)
N(4)-Mo(2)-C(51A)
N(4)-Mo(2)-C(51)
C(51A)-Mo(2)-C(51)
N(4)-Mo(2)-O(2)
C(51A)-Mo(2)-O(2)
C(51)-Mo(2)-O(2)
N(4)-Mo(2)-N(5)
C(51A)-Mo(2)-N(5)
C(51)-Mo(2)-N(5)
O(2)-Mo(2)-N(5)
N(4)-Mo(2)-N(6)
C(51A)-Mo(2)-N(6)
C(51)-Mo(2)-N(6)
O(2)-Mo(2)-N(6)
N(5)-Mo(2)-N(6)
C(52)-C(51)-Mo(2)
C(52)-C(51)-H(51)
Mo(2)-C(51)-H(51)
C(52)-C(51)-H(51A)
Mo(2)-C(51)-H(51A)
H(51)-C(51)-H(51A)
C(51)-C(52)-C(55)
C(51)-C(52)-C(53)
C(55)-C(52)-C(53)
C(51)-C(52)-C(54)
C(55)-C(52)-C(54)
C(53)-C(52)-C(54)
C(60)-C(55)-C(56)
C(60)-C(55)-C(52)
C(56)-C(55)-C(52)
C(57)-C(56)-C(55)
C(57)-C(56)-H(56)
C(55)-C(56)-H(56)
C(58)-C(57)-C(56)
C(58)-C(57)-H(57)
C(56)-C(57)-H(57)
117.56(12)
122.71(13)
116.14(12)
121.58(11)
122.25(11)
118.14(12)
119.67(13)
122.18(13)
119.32(14)
120.69(15)
119.99(13)
120.32(13)
119.94(14)
119.73(13)
119.30(13)
121.32(12)
119.37(13)
118.20(11)
119.21(11)
122.58(12)
94.7(5)
100.9(3)
6.3(7)
151.12(4)
111.7(5)
105.5(3)
99.89(4)
103.1(5)
101.8(4)
85.92(4)
88.65(4)
93.5(5)
93.6(4)
78.47(4)
160.52(4)
136.3(7)
109(3)
114(2)
121(4)
102(4)
13(6)
111.4(6)
110.8(6)
108.3(7)
104.8(8)
112.0(8)
109.6(8)
117.7(6)
122.9(7)
119.2(6)
121.1(7)
119.4
119.4
120.7(8)
119.7
119.7
C(59)-C(58)-C(57)
C(59)-C(58)-H(58)
C(57)-C(58)-H(58)
C(58)-C(59)-C(60)
C(58)-C(59)-H(59)
C(60)-C(59)-H(59)
C(55)-C(60)-C(59)
C(55)-C(60)-H(60)
C(59)-C(60)-H(60)
C(52A)-C(51A)-Mo(2)
C(52A)-C(51A)-H(51)
Mo(2)-C(51A)-H(51)
C(52A)-C(51A)-H(51A)
Mo(2)-C(51A)-H(51A)
H(51)-C(51A)-H(51A)
C(51A)-C(52A)-C(55A)
C(51A)-C(52A)-C(53A)
C(55A)-C(52A)-C(53A)
C(51A)-C(52A)-C(54A)
C(55A)-C(52A)-C(54A)
C(53A)-C(52A)-C(54A)
C(52A)-C(53A)-H(53D)
C(52A)-C(53A)-H(53E)
H(53D)-C(53A)-H(53E)
C(52A)-C(53A)-H(53F)
H(53D)-C(53A)-H(53F)
H(53E)-C(53A)-H(53F)
C(52A)-C(54A)-H(54D)
C(52A)-C(54A)-H(54E)
H(54D)-C(54A)-H(54E)
C(52A)-C(54A)-H(54F)
H(54D)-C(54A)-H(54F)
H(54E)-C(54A)-H(54F)
C(60A)-C(55A)-C(56A)
C(60A)-C(55A)-C(52A)
C(56A)-C(55A)-C(52A)
C(57A)-C(56A)-C(55A)
C(57A)-C(56A)-H(56A)
C(55A)-C(56A)-H(56A)
C(58A)-C(57A)-C(56A)
C(58A)-C(57A)-H(57A)
C(56A)-C(57A)-H(57A)
C(57A)-C(58A)-C(59A)
C(57A)-C(58A)-H(58A)
C(59A)-C(58A)-H(58A)
C(60A)-C(59A)-C(58A)
C(60A)-C(59A)-H(59A)
C(58A)-C(59A)-H(59A)
C(55A)-C(60A)-C(59A)
C(55A)-C(60A)-H(60A)
C(59A)-C(60A)-H(60A)
C(61A)-N(4)-C(61)
C(61A)-N(4)-Mo(2)
C(61)-N(4)-Mo(2)
C(62)-C(61)-C(66)
C(62)-C(61)-N(4)
119.1(8)
120.5
120.5
120.9(8)
119.6
119.6
120.4(7)
119.8
119.8
141.2(9)
113(2)
106(2)
123(4)
96(3)
11(5)
111.8(8)
108.7(8)
108.3(8)
105.9(9)
113.1(9)
108.8(9)
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
117.7(7)
123.6(8)
118.7(8)
121.1(8)
119.5
119.5
119.6(9)
120.2
120.2
120.4(9)
119.8
119.8
119.3(8)
120.3
120.3
122.0(9)
119.0
119.0
5.7(5)
167.9(3)
164.2(3)
116.1(6)
123.1(6)
C(66)-C(61)-N(4)
F(62)-C(62)-C(61)
F(62)-C(62)-C(63)
C(61)-C(62)-C(63)
F(63)-C(63)-C(64)
F(63)-C(63)-C(62)
C(64)-C(63)-C(62)
F(64)-C(64)-C(63)
F(64)-C(64)-C(65)
C(63)-C(64)-C(65)
F(65)-C(65)-C(64)
F(65)-C(65)-C(66)
C(64)-C(65)-C(66)
F(66)-C(66)-C(65)
F(66)-C(66)-C(61)
C(65)-C(66)-C(61)
N(4)-C(61A)-C(66A)
N(4)-C(61A)-C(62A)
C(66A)-C(61A)-C(62A)
F(62A)-C(62A)-C(63A)
F(62A)-C(62A)-C(61A)
C(63A)-C(62A)-C(61A)
F(63A)-C(63A)-C(62A)
F(63A)-C(63A)-C(64A)
C(62A)-C(63A)-C(64A)
F(64A)-C(64A)-C(65A)
F(64A)-C(64A)-C(63A)
C(65A)-C(64A)-C(63A)
F(65A)-C(65A)-C(66A)
F(65A)-C(65A)-C(64A)
C(66A)-C(65A)-C(64A)
F(66A)-C(66A)-C(65A)
F(66A)-C(66A)-C(61A)
C(65A)-C(66A)-C(61A)
C(67)-N(6)-Mo(2)
N(6)-C(67)-C(68)
C(67)-C(68)-H(68A)
C(67)-C(68)-H(68B)
H(68A)-C(68)-H(68B)
C(67)-C(68)-H(68C)
H(68A)-C(68)-H(68C)
H(68B)-C(68)-H(68C)
C(75)-N(5)-C(72)
C(75)-N(5)-Mo(2)
C(72)-N(5)-Mo(2)
C(72)-C(71)-H(71A)
C(72)-C(71)-H(71B)
H(71A)-C(71)-H(71B)
C(72)-C(71)-H(71C)
H(71A)-C(71)-H(71C)
H(71B)-C(71)-H(71C)
C(73)-C(72)-N(5)
C(73)-C(72)-C(71)
N(5)-C(72)-C(71)
C(72)-C(73)-C(74)
C(72)-C(73)-H(73)
120.8(6)
119.9(7)
118.5(7)
121.5(7)
119.7(7)
120.2(7)
120.1(7)
121.3(7)
117.9(7)
120.8(6)
121.6(7)
119.9(7)
118.5(7)
118.3(8)
118.8(8)
122.9(7)
120.6(6)
122.1(6)
117.3(7)
118.6(7)
119.7(7)
121.7(6)
120.0(6)
120.8(6)
119.2(6)
121.6(6)
118.4(6)
120.0(6)
120.5(7)
118.8(7)
120.6(7)
119.3(7)
119.6(8)
121.2(7)
173.30(10)
178.86(16)
109.5
109.5
109.5
109.5
109.5
109.5
106.95(9)
129.23(8)
120.84(8)
109.5
109.5
109.5
109.5
109.5
109.5
109.14(11)
128.29(11)
122.37(10)
107.20(11)
126.4
C(74)-C(73)-H(73)
C(75)-C(74)-C(73)
C(75)-C(74)-H(74)
C(73)-C(74)-H(74)
C(74)-C(75)-N(5)
C(74)-C(75)-C(76)
N(5)-C(75)-C(76)
C(75)-C(76)-H(76A)
C(75)-C(76)-H(76B)
H(76A)-C(76)-H(76B)
C(75)-C(76)-H(76C)
H(76A)-C(76)-H(76C)
H(76B)-C(76)-H(76C)
C(81)-O(2)-Mo(2)
O(2)-C(81)-C(86)
O(2)-C(81)-C(82)
C(86)-C(81)-C(82)
C(83)-C(82)-C(81)
C(83)-C(82)-C(93)
C(81)-C(82)-C(93)
C(84)-C(83)-C(82)
C(84)-C(83)-H(83)
C(82)-C(83)-H(83)
C(83)-C(84)-C(85)
C(83)-C(84)-H(84)
C(85)-C(84)-H(84)
C(84)-C(85)-C(86)
C(84)-C(85)-H(85)
C(86)-C(85)-H(85)
C(85)-C(86)-C(81)
C(85)-C(86)-C(87)
C(81)-C(86)-C(87)
C(88)-C(87)-C(92)
C(88)-C(87)-C(86)
C(92)-C(87)-C(86)
F(88)-C(88)-C(89)
F(88)-C(88)-C(87)
C(89)-C(88)-C(87)
F(89)-C(89)-C(88)
F(89)-C(89)-C(90)
C(88)-C(89)-C(90)
F(90)-C(90)-C(91)
F(90)-C(90)-C(89)
C(91)-C(90)-C(89)
F(91)-C(91)-C(90)
F(91)-C(91)-C(92)
C(90)-C(91)-C(92)
F(92)-C(92)-C(91)
F(92)-C(92)-C(87)
C(91)-C(92)-C(87)
C(98)-C(93)-C(94)
C(98)-C(93)-C(82)
C(94)-C(93)-C(82)
F(94)-C(94)-C(95)
F(94)-C(94)-C(93)
C(95)-C(94)-C(93)
126.4
107.27(11)
126.4
126.4
109.44(11)
126.50(11)
124.06(11)
109.5
109.5
109.5
109.5
109.5
109.5
136.15(7)
120.13(11)
121.07(11)
118.73(11)
119.87(13)
119.75(12)
120.30(11)
120.84(13)
119.6
119.6
119.71(12)
120.1
120.1
120.59(13)
119.7
119.7
120.25(13)
120.64(12)
118.99(11)
116.06(13)
121.60(12)
122.33(13)
117.62(14)
119.91(13)
122.44(13)
120.06(14)
120.10(15)
119.82(15)
120.66(14)
119.66(16)
119.68(14)
119.94(15)
120.53(15)
119.52(13)
118.46(12)
119.07(13)
122.46(14)
116.01(12)
122.48(11)
121.45(12)
118.08(12)
119.49(13)
122.43(13)
F(95)-C(95)-C(96)
F(95)-C(95)-C(94)
C(96)-C(95)-C(94)
F(96)-C(96)-C(95)
F(96)-C(96)-C(97)
C(95)-C(96)-C(97)
F(97)-C(97)-C(98)
F(97)-C(97)-C(96)
C(98)-C(97)-C(96)
F(98)-C(98)-C(97)
F(98)-C(98)-C(93)
C(97)-C(98)-C(93)
C(2S)-C(1S)-H(1S1)
C(2S)-C(1S)-H(1S2)
H(1S1)-C(1S)-H(1S2)
C(2S)-C(1S)-H(1S3)
H(1S1)-C(1S)-H(1S3)
H(1S2)-C(1S)-H(1S3)
O(1S)-C(2S)-C(1S)
O(1S)-C(2S)-H(2S1)
C(1S)-C(2S)-H(2S1)
O(1S)-C(2S)-H(2S2)
C(1S)-C(2S)-H(2S2)
H(2S1)-C(2S)-H(2S2)
C(3S)-O(1S)-C(2S)
O(1S)-C(3S)-C(4S)
O(1S)-C(3S)-H(3S1)
C(4S)-C(3S)-H(3S1)
O(1S)-C(3S)-H(3S2)
C(4S)-C(3S)-H(3S2)
H(3S1)-C(3S)-H(3S2)
C(3S)-C(4S)-H(4S1)
C(3S)-C(4S)-H(4S2)
H(4S1)-C(4S)-H(4S2)
C(3S)-C(4S)-H(4S3)
H(4S1)-C(4S)-H(4S3)
H(4S2)-C(4S)-H(4S3)
C(2SA)-C(1SA)-H(1S4)
C(2SA)-C(1SA)-H(1S5)
H(1S4)-C(1SA)-H(1S5)
C(2SA)-C(1SA)-H(1S6)
H(1S4)-C(1SA)-H(1S6)
H(1S5)-C(1SA)-H(1S6)
O(1SA)-C(2SA)-C(1SA)
O(1SA)-C(2SA)-H(2S3)
C(1SA)-C(2SA)-H(2S3)
O(1SA)-C(2SA)-H(2S4)
C(1SA)-C(2SA)-H(2S4)
H(2S3)-C(2SA)-H(2S4)
C(2SA)-O(1SA)-C(3SA)
O(1SA)-C(3SA)-C(4SA)
O(1SA)-C(3SA)-H(3S3)
C(4SA)-C(3SA)-H(3S3)
O(1SA)-C(3SA)-H(3S4)
C(4SA)-C(3SA)-H(3S4)
H(3S3)-C(3SA)-H(3S4)
119.40(14)
120.80(13)
119.80(13)
120.59(13)
119.89(13)
119.52(13)
120.68(12)
119.42(13)
119.89(13)
117.89(12)
119.70(12)
122.33(12)
109.5
109.5
109.5
109.5
109.5
109.5
108.2(7)
110.1
110.1
110.1
110.1
108.4
111.9(4)
109.8(3)
109.7
109.7
109.7
109.7
108.2
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.3(8)
109.8
109.8
109.8
109.8
108.3
113.4(4)
113.8(4)
108.8
108.8
108.8
108.8
107.7
C(3SA)-C(4SA)-H(4S4)
109.5
C(3SA)-C(4SA)-H(4S5)
109.5
H(4S4)-C(4SA)-H(4S5)
109.5
C(3SA)-C(4SA)-H(4S6)
109.5
H(4S4)-C(4SA)-H(4S6)
109.5
H(4S5)-C(4SA)-H(4S6)
109.5
_____________________________________________________________
Table S4. Anisotropic displacement parameters (Å2x 103) for 2b'. The anisotropic
displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11
U22
U33
U23
U13
U12
______________________________________________________________________________
Mo(1)
15(1)
14(1)
14(1)
1(1)
3(1)
0(1)
C(1)
20(1)
19(1)
19(1)
3(1)
6(1)
2(1)
C(2)
24(1)
22(1)
18(1)
1(1)
7(1)
4(1)
C(3)
31(1)
42(1)
25(1)
4(1)
14(1)
12(1)
C(4)
39(1)
20(1)
25(1)
2(1)
8(1)
3(1)
C(5)
23(1)
21(1)
15(1)
2(1)
7(1)
1(1)
C(6)
26(1)
24(1)
18(1)
3(1)
5(1)
-3(1)
C(7)
35(1)
23(1)
22(1)
6(1)
9(1)
0(1)
C(8)
32(1)
32(1)
22(1)
10(1)
9(1)
7(1)
C(9)
24(1)
34(1)
19(1)
5(1)
5(1)
1(1)
C(10)
25(1)
23(1)
19(1)
1(1)
6(1)
-2(1)
N(1)
17(1)
17(1)
18(1)
2(1)
4(1)
1(1)
C(11)
17(1)
20(1)
17(1)
2(1)
5(1)
3(1)
C(12)
17(1)
20(1)
28(1)
1(1)
5(1)
3(1)
F(12)
21(1)
19(1)
54(1)
-3(1)
-1(1)
3(1)
C(13)
20(1)
25(1)
31(1)
6(1)
9(1)
8(1)
F(13)
26(1)
27(1)
58(1)
12(1)
8(1)
12(1)
C(14)
18(1)
35(1)
20(1)
5(1)
6(1)
9(1)
F(14)
23(1)
48(1)
28(1)
5(1)
1(1)
15(1)
C(15)
19(1)
30(1)
18(1)
-4(1)
3(1)
2(1)
F(15)
24(1)
36(1)
34(1)
-13(1)
-6(1)
3(1)
C(16)
20(1)
21(1)
19(1)
-1(1)
4(1)
3(1)
F(16)
26(1)
19(1)
36(1)
-2(1)
1(1)
1(1)
N(3)
21(1)
22(1)
19(1)
6(1)
2(1)
2(1)
C(17)
28(1)
25(1)
30(1)
12(1)
2(1)
1(1)
C(18)
55(1)
25(1)
86(2)
24(1)
10(1)
-4(1)
N(2)
19(1)
16(1)
18(1)
2(1)
4(1)
-1(1)
C(21)
21(1)
45(1)
26(1)
8(1)
10(1)
4(1)
C(22)
21(1)
27(1)
20(1)
3(1)
6(1)
-3(1)
C(23)
31(1)
36(1)
26(1)
11(1)
8(1)
-6(1)
C(24)
35(1)
25(1)
26(1)
11(1)
2(1)
-3(1)
C(25)
25(1)
15(1)
22(1)
3(1)
2(1)
0(1)
C(26)
30(1)
21(1)
35(1)
7(1)
7(1)
9(1)
O(1)
18(1)
14(1)
17(1)
1(1)
2(1)
0(1)
C(31)
20(1)
15(1)
14(1)
3(1)
1(1)
0(1)
C(32)
23(1)
16(1)
16(1)
4(1)
3(1)
3(1)
C(33)
31(1)
16(1)
19(1)
1(1)
3(1)
3(1)
C(34)
31(1)
17(1)
21(1)
0(1)
2(1)
-4(1)
C(35)
24(1)
22(1)
21(1)
3(1)
3(1)
-5(1)
C(36)
20(1)
19(1)
17(1)
2(1)
3(1)
-1(1)
C(37)
17(1)
24(1)
21(1)
0(1)
5(1)
-2(1)
C(38)
18(1)
31(1)
26(1)
6(1)
8(1)
-1(1)
F(38)
32(1)
35(1)
32(1)
13(1)
14(1)
3(1)
C(39)
22(1)
44(1)
26(1)
5(1)
13(1)
1(1)
F(39)
40(1)
63(1)
33(1)
13(1)
25(1)
10(1)
C(40)
20(1)
42(1)
32(1)
-2(1)
12(1)
5(1)
F(40)
36(1)
56(1)
40(1)
0(1)
22(1)
16(1)
C(41)
19(1)
31(1)
30(1)
0(1)
6(1)
4(1)
F(41)
33(1)
34(1)
39(1)
1(1)
10(1)
13(1)
C(42)
19(1)
26(1)
21(1)
0(1)
4(1)
0(1)
F(42)
34(1)
27(1)
20(1)
3(1)
5(1)
6(1)
C(43)
C(44)
F(44)
C(45)
F(45)
C(46)
F(46)
C(47)
F(47)
C(48)
F(48)
Mo(2)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(57)
C(58)
C(59)
C(60)
C(51A)
C(52A)
C(53A)
C(54A)
C(55A)
C(56A)
C(57A)
C(58A)
C(59A)
C(60A)
N(4)
C(61)
C(62)
F(62)
C(63)
F(63)
C(64)
F(64)
C(65)
F(65)
C(66)
F(66)
C(61A)
C(62A)
F(62A)
C(63A)
F(63A)
C(64A)
F(64A)
C(65A)
F(65A)
C(66A)
F(66A)
N(6)
22(1)
31(1)
43(1)
31(1)
41(1)
23(1)
25(1)
25(1)
30(1)
22(1)
23(1)
14(1)
12(2)
22(2)
23(2)
35(4)
21(2)
19(2)
35(3)
43(4)
44(3)
30(3)
22(2)
15(2)
25(2)
27(3)
18(2)
29(3)
34(3)
39(4)
39(3)
31(4)
19(1)
24(2)
52(4)
96(5)
68(4)
138(5)
61(4)
108(4)
46(3)
70(3)
34(3)
45(2)
24(3)
39(3)
75(4)
50(4)
106(5)
48(3)
75(3)
40(3)
85(4)
24(3)
41(3)
22(1)
19(1)
25(1)
33(1)
39(1)
65(1)
41(1)
62(1)
31(1)
47(1)
24(1)
32(1)
13(1)
12(2)
13(2)
42(3)
23(2)
24(2)
16(2)
25(2)
28(2)
44(3)
22(2)
22(2)
28(2)
24(3)
16(2)
18(2)
33(2)
20(2)
28(2)
23(2)
28(2)
20(1)
38(2)
34(2)
34(2)
48(2)
52(2)
65(3)
113(4)
68(3)
92(5)
37(3)
44(3)
15(2)
24(2)
14(2)
25(2)
28(2)
38(2)
55(2)
30(2)
44(2)
23(2)
20(2)
18(1)
18(1)
28(1)
53(1)
37(1)
79(1)
30(1)
50(1)
25(1)
46(1)
21(1)
39(1)
15(1)
12(2)
18(2)
31(3)
25(3)
16(2)
20(2)
24(3)
26(4)
17(2)
22(3)
18(3)
24(3)
44(4)
35(5)
20(3)
24(3)
29(4)
17(3)
16(3)
19(3)
19(1)
14(2)
30(2)
44(2)
38(2)
64(3)
30(2)
35(2)
19(2)
30(2)
31(2)
29(3)
26(2)
32(2)
52(3)
38(2)
65(3)
24(2)
31(2)
27(2)
27(2)
13(2)
23(2)
19(1)
2(1)
8(1)
24(1)
9(1)
33(1)
3(1)
11(1)
7(1)
23(1)
6(1)
20(1)
2(1)
3(2)
1(1)
6(2)
11(2)
9(1)
4(1)
6(2)
-3(3)
12(2)
6(2)
-1(2)
12(2)
-1(2)
6(2)
4(2)
11(2)
3(2)
6(2)
7(2)
13(2)
2(1)
-3(2)
-6(1)
4(1)
-12(2)
-23(2)
-15(2)
-23(2)
-1(2)
8(3)
-2(2)
4(2)
1(2)
-1(2)
-1(2)
-11(2)
-22(2)
-6(2)
-18(2)
-2(1)
6(2)
-2(1)
0(1)
2(1)
3(1)
5(1)
10(1)
6(1)
15(1)
9(1)
17(1)
9(1)
18(1)
4(1)
8(1)
4(1)
2(1)
4(1)
1(2)
2(2)
2(2)
-1(2)
-1(2)
-1(3)
6(2)
3(3)
6(2)
3(2)
7(2)
1(3)
-2(2)
8(2)
2(3)
1(2)
2(2)
4(2)
5(1)
6(2)
9(2)
25(2)
15(2)
30(3)
14(2)
25(2)
18(2)
28(2)
10(2)
13(2)
7(2)
22(2)
43(3)
20(3)
51(3)
17(2)
25(2)
13(2)
31(2)
7(2)
13(2)
3(1)
6(1)
12(1)
17(1)
20(1)
37(1)
12(1)
17(1)
6(1)
7(1)
7(1)
10(1)
1(1)
4(1)
1(1)
23(2)
3(2)
8(1)
0(1)
2(2)
4(2)
14(2)
2(2)
-4(2)
8(1)
1(2)
-3(2)
-2(1)
0(2)
-9(2)
-2(2)
-6(2)
1(2)
2(1)
4(2)
15(2)
23(2)
20(2)
30(3)
21(3)
39(3)
4(4)
5(5)
-1(3)
-13(2)
2(2)
1(2)
-4(2)
-1(2)
-12(2)
7(2)
3(2)
2(2)
5(2)
-1(2)
-6(2)
1(1)
C(67)
26(1)
20(1)
18(1)
2(1)
3(1)
0(1)
C(68)
40(1)
23(1)
35(1)
4(1)
7(1)
-11(1)
N(5)
15(1)
16(1)
19(1)
2(1)
5(1)
2(1)
C(71)
21(1)
23(1)
26(1)
0(1)
8(1)
7(1)
C(72)
16(1)
21(1)
20(1)
1(1)
6(1)
4(1)
C(73)
15(1)
38(1)
33(1)
-10(1)
5(1)
3(1)
C(74)
18(1)
30(1)
31(1)
-10(1)
5(1)
-1(1)
C(75)
17(1)
18(1)
22(1)
0(1)
6(1)
2(1)
C(76)
20(1)
26(1)
34(1)
-6(1)
7(1)
5(1)
O(2)
23(1)
16(1)
18(1)
3(1)
7(1)
0(1)
C(81)
23(1)
18(1)
14(1)
2(1)
4(1)
-2(1)
C(82)
27(1)
19(1)
16(1)
4(1)
3(1)
0(1)
C(83)
34(1)
22(1)
21(1)
8(1)
3(1)
-2(1)
C(84)
35(1)
29(1)
23(1)
10(1)
6(1)
-7(1)
C(85)
29(1)
32(1)
21(1)
4(1)
9(1)
-6(1)
C(86)
25(1)
23(1)
18(1)
1(1)
7(1)
-3(1)
C(87)
25(1)
26(1)
22(1)
-1(1)
12(1)
-2(1)
C(88)
21(1)
31(1)
34(1)
-5(1)
14(1)
0(1)
F(88)
21(1)
37(1)
45(1)
-13(1)
6(1)
-2(1)
C(89)
21(1)
40(1)
44(1)
-1(1)
16(1)
7(1)
F(89)
21(1)
58(1)
68(1)
-3(1)
10(1)
16(1)
C(90)
34(1)
32(1)
46(1)
3(1)
27(1)
10(1)
F(90)
43(1)
38(1)
73(1)
7(1)
35(1)
18(1)
C(91)
36(1)
26(1)
36(1)
-4(1)
23(1)
-2(1)
F(91)
50(1)
26(1)
48(1)
-10(1)
26(1)
-4(1)
C(92)
28(1)
28(1)
23(1)
-2(1)
12(1)
-3(1)
F(92)
35(1)
33(1)
25(1)
-2(1)
4(1)
-6(1)
C(93)
29(1)
18(1)
18(1)
5(1)
4(1)
4(1)
C(94)
31(1)
19(1)
24(1)
2(1)
2(1)
3(1)
F(94)
34(1)
25(1)
34(1)
-6(1)
4(1)
-1(1)
C(95)
38(1)
21(1)
28(1)
0(1)
7(1)
9(1)
F(95)
48(1)
31(1)
43(1)
-12(1)
14(1)
8(1)
C(96)
32(1)
25(1)
28(1)
7(1)
9(1)
12(1)
F(96)
36(1)
38(1)
42(1)
5(1)
16(1)
16(1)
C(97)
27(1)
24(1)
23(1)
6(1)
3(1)
4(1)
F(97)
27(1)
35(1)
32(1)
2(1)
5(1)
0(1)
C(98)
30(1)
20(1)
17(1)
4(1)
4(1)
3(1)
F(98)
33(1)
27(1)
22(1)
-4(1)
7(1)
-2(1)
C(1S)
92(6)
53(5)
40(3)
9(4)
28(4)
44(5)
C(2S)
64(3)
64(4)
44(2)
1(3)
6(2)
36(4)
O(1S)
42(1)
39(2)
58(2)
3(1)
8(1)
16(1)
C(3S)
36(2)
56(2)
74(3)
1(2)
8(2)
10(2)
C(4S)
56(3)
36(2)
102(4)
19(2)
30(3)
15(2)
C(1SA) 105(10)
34(3)
42(3)
4(3)
31(7)
25(5)
C(2SA)
48(3)
55(4)
44(3)
10(3)
18(2)
27(3)
O(1SA)
39(2)
32(2)
44(2)
9(1)
19(1)
10(1)
C(3SA)
43(2)
28(2)
50(2)
4(1)
23(2)
7(1)
C(4SA)
85(5)
50(3)
71(4)
26(3)
55(4)
26(3)
______________________________________________________________________________
Table S5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for 2b'.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
H(1)
H(3A)
H(3B)
H(3C)
H(4A)
H(4B)
H(4C)
H(6)
H(7)
H(8)
H(9)
H(10)
H(18A)
H(18B)
H(18C)
H(21A)
H(21B)
H(21C)
H(23)
H(24)
H(26A)
H(26B)
H(26C)
H(33)
H(34)
H(35)
H(51)
H(53A)
H(53B)
H(53C)
H(54A)
H(54B)
H(54C)
H(56)
H(57)
H(58)
H(59)
H(60)
H(51A)
H(53D)
H(53E)
H(53F)
H(54D)
H(54E)
H(54F)
H(56A)
H(57A)
H(58A)
H(59A)
H(60A)
7779(12)
7585
8280
8265
5196
6408
5780
7174
6087
4224
3476
4541
8575
7320
8213
3348
4072
3232
4327
6263
8035
8188
7533
8353
10289
11008
7420(40)
5278
5386
6049
8005
7388
8495
5669
5065
5404
6425
7116
7600(50)
5497
6130
5322
8535
8152
7455
5754
5073
5521
6529
7238
7722(10)
7086
7055
7924
6511
6204
6221
9000
9844
9272
7845
7001
11209
11361
11114
7265
8091
7387
6349
5906
6303
7219
6448
10967
11375
10513
7910(30)
7771
8482
8679
9210
9042
8655
6474
5447
5732
7041
8069
7840(40)
8523
8653
7771
8639
9161
9083
6463
5455
5741
7064
8057
2378(7)
802
1520
1287
1455
1654
924
1412
864
123
-73
499
3113
2728
2356
2713
3203
3418
4001
4067
3595
3437
2881
4822
4762
4133
8185(13)
7428
7008
7754
7577
6826
7119
7028
6139
5192
5152
6055
8139(15)
6935
7683
7313
7001
7529
6794
6938
6030
5108
5067
5981
24
47
47
47
44
44
44
29
33
34
32
29
87
87
87
46
46
46
39
37
43
43
43
28
31
30
14
47
47
47
44
44
44
24
37
43
41
31
27
49
49
49
43
43
43
35
38
37
35
32
H(68A)
6308
4154
7950
54
H(68B)
5406
4334
7332
54
H(68C)
5361
4687
8023
54
H(71A)
11242
7186
7420
35
H(71B)
10965
6544
7874
35
H(71C)
12311
6990
7948
35
H(73)
13155
8340
8828
37
H(74)
12224
9350
9363
35
H(76A)
10088
9516
9281
42
H(76B)
9193
8631
9135
42
H(76C)
9193
9171
8583
42
H(83)
8769
4377
9424
33
H(84)
7128
4451
9784
37
H(85)
6368
5635
9746
35
H(1S1)
1857
5041
6976
84
H(1S2)
972
5030
6291
84
H(1S3)
1055
5706
6879
84
H(2S1)
3009
6313
6922
68
H(2S2)
2934
5631
6336
68
H(3S1)
3166
6544
5655
69
H(3S2)
3378
7300
6214
69
H(4S1)
2734
7697
5222
93
H(4S2)
1774
7745
5598
93
H(4S3)
1544
6985
5043
93
H(1S4)
2411
5176
6877
86
H(1S5)
1286
5182
6295
86
H(1S6)
1446
5674
6984
86
H(2S3)
3158
6593
6921
55
H(2S4)
2989
6102
6229
55
H(3S3)
3066
7736
6428
46
H(3S4)
1804
7839
6013
46
H(4S4)
3086
7801
5388
89
H(4S5)
1981
7022
5131
89
H(4S6)
3242
6913
5547
89
________________________________________________________________________________
Table S6. Crystal data and structure refinement for 3.
Identification code
X8_12143
Empirical formula
C44 H10 F25 Mo N O2
Formula weight
1155.47
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Monoclinic
Space group
P21/c
Unit cell dimensions
a = 11.9310(11) Å
= 90°.
b = 43.920(4) Å
= 105.667(2)°.
c = 7.9516(7) Å
 = 90°.
Å3
Volume
4011.9(6)
Z
4
Density (calculated)
1.913 Mg/m3
Absorption coefficient
0.487 mm-1
F(000)
2256
Crystal size
0.25 x 0.08 x 0.01 mm3
Theta range for data collection
1.77 to 26.02°.
Index ranges
-14<=h<=8, -53<=k<=54, -9<=l<=9
Reflections collected
35662
Independent reflections
7820 [Rint = 0.0504]
Completeness to theta = 26.02°
98.9 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9951 and 0.8879
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
7820 / 5 / 670
Goodness-of-fit on
F2
1.180
Final R indices [I>2σ(I)]
R1 = 0.0538, wR2 = 0.0975
R indices (all data)
R1 = 0.0671, wR2 = 0.1014
Largest diff. peak and hole
0.477 and -0.744 e.Å-3
Table S7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for 3. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
Mo(1)
6352(1)
6207(1)
6719(1)
17(1)
C(1)
7303(3)
6383(1)
9225(5)
22(1)
C(2)
6580(4)
6140(1)
9456(5)
23(1)
N(1)
7369(3)
5942(1)
6512(4)
21(1)
C(11)
8248(3)
5751(1)
6347(5)
21(1)
C(12)
8389(3)
5670(1)
4722(5)
20(1)
C(13)
9270(4)
5486(1)
4561(5)
23(1)
C(14)
10066(3)
5374(1)
6051(6)
23(1)
C(15)
9944(4)
5450(1)
7666(6)
30(1)
C(16)
9063(4)
5635(1)
7826(5)
28(1)
F(1)
7632(2)
5782(1)
3283(3)
26(1)
F(2)
9405(2)
5416(1)
2986(3)
32(1)
F(3)
10940(2)
5196(1)
5905(3)
35(1)
F(4)
10711(2)
5343(1)
9115(3)
44(1)
F(5)
8953(2)
5712(1)
9407(3)
40(1)
O(1)
6475(2)
6600(1)
5649(3)
17(1)
C(21)
6911(3)
6880(1)
6124(5)
20(1)
C(22)
6172(3)
7123(1)
6211(5)
19(1)
C(23)
6647(4)
7413(1)
6664(5)
26(1)
C(24)
7829(4)
7462(1)
7027(6)
34(1)
C(25)
8565(4)
7223(1)
6910(6)
31(1)
C(26)
8111(3)
6932(1)
6437(5)
23(1)
C(27)
4887(3)
7087(1)
5833(5)
18(1)
C(28)
4127(4)
7278(1)
4649(5)
22(1)
C(29)
2934(4)
7277(1)
4416(5)
24(1)
C(30)
2455(3)
7073(1)
5324(5)
26(1)
C(31)
3168(3)
6872(1)
6466(5)
22(1)
C(32)
4350(3)
6886(1)
6703(5)
20(1)
C(33)
8900(3)
6681(1)
6223(5)
22(1)
C(34)
8846(3)
6556(1)
4598(5)
24(1)
C(35)
9589(3)
6330(1)
4375(5)
24(1)
C(36)
10435(3)
6222(1)
5806(5)
24(1)
C(37)
10505(3)
6338(1)
7435(5)
26(1)
C(38)
9752(3)
6564(1)
7625(5)
23(1)
F(6)
4555(2)
7471(1)
3667(3)
27(1)
F(7)
2254(2)
7474(1)
3298(3)
32(1)
F(8)
1302(2)
7068(1)
5117(3)
36(1)
F(9)
2707(2)
6674(1)
7376(3)
32(1)
F(10)
5012(2)
6698(1)
7927(3)
24(1)
F(11)
8064(2)
6662(1)
3183(3)
31(1)
F(12)
9497(2)
6210(1)
2793(3)
31(1)
F(13)
11172(2)
6004(1)
5608(3)
32(1)
F(14)
11314(2)
6229(1)
8833(3)
34(1)
F(15)
9842(2)
6672(1)
9244(3)
32(1)
O(2)
4721(2)
6103(1)
6252(3)
19(1)
C(41)
3993(3)
5893(1)
5269(5)
17(1)
C(42)
3284(3)
5979(1)
3614(5)
19(1)
C(43)
2464(3)
5776(1)
2677(5)
21(1)
C(44)
2363(3)
5487(1)
3302(5)
24(1)
C(45)
3106(3)
5398(1)
4891(5)
21(1)
C(46)
3921(3)
5601(1)
5875(5)
18(1)
C(47)
3463(3)
6277(1)
2859(5)
18(1)
C(48)
2590(3)
6490(1)
2299(5)
20(1)
C(49)
2757(3)
6757(1)
1491(5)
21(1)
C(50)
3824(3)
6821(1)
1251(5)
21(1)
C(51)
4738(3)
6622(1)
1844(5)
20(1)
C(52)
4536(3)
6354(1)
2603(5)
18(1)
C(53)
4729(3)
5498(1)
7568(5)
19(1)
C(54)
4481(3)
5539(1)
9155(5)
23(1)
C(55)
5218(4)
5432(1)
10715(5)
24(1)
C(56)
6223(4)
5284(1)
10673(5)
26(1)
C(57)
6504(4)
5242(1)
9134(5)
26(1)
C(58)
5747(3)
5347(1)
7599(5)
23(1)
F(16)
1537(2)
6440(1)
2559(3)
27(1)
F(17)
1885(2)
6959(1)
954(3)
29(1)
F(18)
3995(2)
7082(1)
482(3)
28(1)
F(19)
5786(2)
6692(1)
1650(3)
25(1)
F(20)
5444(2)
6158(1)
3133(3)
22(1)
F(21)
3513(2)
5686(1)
9220(3)
38(1)
F(22)
4949(2)
5472(1)
12220(3)
40(1)
F(23)
6924(2)
5174(1)
12174(3)
33(1)
F(24)
7494(2)
5101(1)
9109(3)
42(1)
F(25)
6048(2)
5303(1)
6103(3)
34(1)
________________________________________________________________________________
Table S8. Bond lengths [Å] and angles [°] for 3.
_____________________________________________________
Mo(1)-N(1)
1.720(3)
Mo(1)-O(2)
1.935(3)
Mo(1)-O(1)
1.946(3)
Mo(1)-C(2)
2.140(4)
Mo(1)-C(1)
2.153(4)
C(1)-C(2)
1.415(6)
C(1)-H(1A)
0.998(18)
C(1)-H(1B)
0.975(18)
C(2)-H(2A)
0.981(18)
C(2)-H(2B)
0.990(18)
N(1)-C(11)
1.377(5)
C(11)-C(12)
1.394(6)
C(11)-C(16)
1.404(5)
C(12)-F(1)
1.345(4)
C(12)-C(13)
1.359(6)
C(13)-F(2)
1.340(5)
C(13)-C(14)
1.392(5)
C(14)-F(3)
1.334(4)
C(14)-C(15)
1.372(6)
C(15)-F(4)
1.347(4)
C(15)-C(16)
1.362(6)
C(16)-F(5)
1.342(5)
O(1)-C(21)
1.350(5)
C(21)-C(22)
1.398(5)
C(21)-C(26)
1.403(5)
C(22)-C(23)
1.399(6)
C(22)-C(27)
1.489(5)
C(23)-C(24)
1.378(6)
C(23)-H(23)
0.9500
C(24)-C(25)
1.388(6)
C(24)-H(24)
0.9500
C(25)-C(26)
1.400(6)
C(25)-H(25)
0.9500
C(26)-C(33)
1.487(6)
C(27)-C(32)
1.383(5)
C(27)-C(28)
1.398(5)
C(28)-F(6)
1.343(5)
C(28)-C(29)
1.385(6)
C(29)-F(7)
1.343(4)
C(29)-C(30)
1.369(6)
C(30)-F(8)
1.342(5)
C(30)-C(31)
1.382(6)
C(31)-F(9)
1.339(4)
C(31)-C(32)
1.374(5)
C(32)-F(10)
1.354(4)
C(33)-C(34)
1.389(6)
C(33)-C(38)
1.390(5)
C(34)-F(11)
1.336(4)
C(34)-C(35)
1.373(6)
C(35)-F(12)
1.342(5)
C(35)-C(36)
1.386(6)
C(36)-F(13)
1.336(5)
C(36)-C(37)
1.375(6)
C(37)-F(14)
1.348(4)
C(37)-C(38)
C(38)-F(15)
O(2)-C(41)
C(41)-C(46)
C(41)-C(42)
C(42)-C(43)
C(42)-C(47)
C(43)-C(44)
C(43)-H(43)
C(44)-C(45)
C(44)-H(44)
C(45)-C(46)
C(45)-H(45)
C(46)-C(53)
C(47)-C(48)
C(47)-C(52)
C(48)-F(16)
C(48)-C(49)
C(49)-F(17)
C(49)-C(50)
C(50)-F(18)
C(50)-C(51)
C(51)-F(19)
C(51)-C(52)
C(52)-F(20)
C(53)-C(58)
C(53)-C(54)
C(54)-F(21)
C(54)-C(55)
C(55)-F(22)
C(55)-C(56)
C(56)-F(23)
C(56)-C(57)
C(57)-F(24)
C(57)-C(58)
C(58)-F(25)
N(1)-Mo(1)-O(2)
N(1)-Mo(1)-O(1)
O(2)-Mo(1)-O(1)
N(1)-Mo(1)-C(2)
O(2)-Mo(1)-C(2)
O(1)-Mo(1)-C(2)
N(1)-Mo(1)-C(1)
O(2)-Mo(1)-C(1)
O(1)-Mo(1)-C(1)
C(2)-Mo(1)-C(1)
C(2)-C(1)-Mo(1)
C(2)-C(1)-H(1A)
Mo(1)-C(1)-H(1A)
C(2)-C(1)-H(1B)
Mo(1)-C(1)-H(1B)
H(1A)-C(1)-H(1B)
C(1)-C(2)-Mo(1)
C(1)-C(2)-H(2A)
Mo(1)-C(2)-H(2A)
1.371(6)
1.349(5)
1.360(4)
1.380(5)
1.410(5)
1.383(5)
1.482(5)
1.380(6)
0.9500
1.389(5)
0.9500
1.395(5)
0.9500
1.499(5)
1.380(5)
1.391(5)
1.346(4)
1.379(6)
1.345(4)
1.366(6)
1.339(4)
1.377(5)
1.337(4)
1.374(5)
1.359(4)
1.379(6)
1.383(6)
1.337(5)
1.394(5)
1.332(5)
1.373(6)
1.349(4)
1.366(6)
1.337(5)
1.387(5)
1.346(5)
121.37(14)
114.79(14)
108.45(11)
96.00(16)
90.40(13)
124.27(13)
97.00(15)
120.88(14)
90.23(13)
38.49(15)
70.3(2)
122(2)
109(2)
118(2)
113(2)
115(3)
71.2(2)
121(2)
114(2)
C(1)-C(2)-H(2B)
Mo(1)-C(2)-H(2B)
H(2A)-C(2)-H(2B)
C(11)-N(1)-Mo(1)
N(1)-C(11)-C(12)
N(1)-C(11)-C(16)
C(12)-C(11)-C(16)
F(1)-C(12)-C(13)
F(1)-C(12)-C(11)
C(13)-C(12)-C(11)
F(2)-C(13)-C(12)
F(2)-C(13)-C(14)
C(12)-C(13)-C(14)
F(3)-C(14)-C(15)
F(3)-C(14)-C(13)
C(15)-C(14)-C(13)
F(4)-C(15)-C(16)
F(4)-C(15)-C(14)
C(16)-C(15)-C(14)
F(5)-C(16)-C(15)
F(5)-C(16)-C(11)
C(15)-C(16)-C(11)
C(21)-O(1)-Mo(1)
O(1)-C(21)-C(22)
O(1)-C(21)-C(26)
C(22)-C(21)-C(26)
C(21)-C(22)-C(23)
C(21)-C(22)-C(27)
C(23)-C(22)-C(27)
C(24)-C(23)-C(22)
C(24)-C(23)-H(23)
C(22)-C(23)-H(23)
C(23)-C(24)-C(25)
C(23)-C(24)-H(24)
C(25)-C(24)-H(24)
C(24)-C(25)-C(26)
C(24)-C(25)-H(25)
C(26)-C(25)-H(25)
C(25)-C(26)-C(21)
C(25)-C(26)-C(33)
C(21)-C(26)-C(33)
C(32)-C(27)-C(28)
C(32)-C(27)-C(22)
C(28)-C(27)-C(22)
F(6)-C(28)-C(29)
F(6)-C(28)-C(27)
C(29)-C(28)-C(27)
F(7)-C(29)-C(30)
F(7)-C(29)-C(28)
C(30)-C(29)-C(28)
F(8)-C(30)-C(29)
F(8)-C(30)-C(31)
C(29)-C(30)-C(31)
F(9)-C(31)-C(32)
F(9)-C(31)-C(30)
C(32)-C(31)-C(30)
118(2)
107(2)
116(3)
175.0(3)
122.1(3)
121.0(4)
116.9(4)
119.7(4)
118.3(3)
122.0(4)
120.9(4)
119.3(4)
119.8(4)
120.4(4)
120.1(4)
119.4(4)
119.4(4)
119.8(4)
120.7(4)
120.7(4)
118.2(4)
121.1(4)
139.0(2)
120.6(3)
119.6(4)
119.7(4)
119.3(4)
122.5(3)
118.2(4)
121.1(4)
119.5
119.5
119.9(4)
120.1
120.1
120.2(4)
119.9
119.9
119.8(4)
119.6(4)
120.6(4)
114.7(4)
123.9(3)
121.1(4)
117.6(3)
119.4(4)
122.9(4)
120.4(4)
120.0(4)
119.5(4)
120.5(4)
119.9(4)
119.7(4)
120.7(4)
120.0(4)
119.2(4)
F(10)-C(32)-C(31)
F(10)-C(32)-C(27)
C(31)-C(32)-C(27)
C(34)-C(33)-C(38)
C(34)-C(33)-C(26)
C(38)-C(33)-C(26)
F(11)-C(34)-C(35)
F(11)-C(34)-C(33)
C(35)-C(34)-C(33)
F(12)-C(35)-C(34)
F(12)-C(35)-C(36)
C(34)-C(35)-C(36)
F(13)-C(36)-C(37)
F(13)-C(36)-C(35)
C(37)-C(36)-C(35)
F(14)-C(37)-C(38)
F(14)-C(37)-C(36)
C(38)-C(37)-C(36)
F(15)-C(38)-C(37)
F(15)-C(38)-C(33)
C(37)-C(38)-C(33)
C(41)-O(2)-Mo(1)
O(2)-C(41)-C(46)
O(2)-C(41)-C(42)
C(46)-C(41)-C(42)
C(43)-C(42)-C(41)
C(43)-C(42)-C(47)
C(41)-C(42)-C(47)
C(44)-C(43)-C(42)
C(44)-C(43)-H(43)
C(42)-C(43)-H(43)
C(43)-C(44)-C(45)
C(43)-C(44)-H(44)
C(45)-C(44)-H(44)
C(44)-C(45)-C(46)
C(44)-C(45)-H(45)
C(46)-C(45)-H(45)
C(41)-C(46)-C(45)
C(41)-C(46)-C(53)
C(45)-C(46)-C(53)
C(48)-C(47)-C(52)
C(48)-C(47)-C(42)
C(52)-C(47)-C(42)
F(16)-C(48)-C(49)
F(16)-C(48)-C(47)
C(49)-C(48)-C(47)
F(17)-C(49)-C(50)
F(17)-C(49)-C(48)
C(50)-C(49)-C(48)
F(18)-C(50)-C(49)
F(18)-C(50)-C(51)
C(49)-C(50)-C(51)
F(19)-C(51)-C(52)
F(19)-C(51)-C(50)
C(52)-C(51)-C(50)
F(20)-C(52)-C(51)
116.7(3)
119.3(3)
123.9(4)
116.0(4)
121.8(4)
122.1(4)
118.1(4)
119.5(4)
122.5(4)
121.0(4)
119.3(4)
119.7(4)
120.2(4)
120.4(4)
119.4(4)
120.7(4)
119.4(4)
119.9(4)
118.2(4)
119.2(4)
122.6(4)
136.4(2)
121.3(3)
118.9(3)
119.8(3)
119.3(4)
120.7(3)
120.0(3)
121.1(3)
119.5
119.5
119.4(4)
120.3
120.3
120.4(4)
119.8
119.8
119.9(3)
120.6(3)
119.5(3)
115.7(4)
123.4(4)
120.8(3)
118.1(3)
119.6(4)
122.3(4)
119.4(4)
120.8(4)
119.8(4)
120.1(3)
119.6(4)
120.3(4)
121.9(3)
119.5(4)
118.6(4)
117.5(3)
F(20)-C(52)-C(47)
119.3(3)
C(51)-C(52)-C(47)
123.2(3)
C(58)-C(53)-C(54)
116.8(3)
C(58)-C(53)-C(46)
120.8(4)
C(54)-C(53)-C(46)
122.4(4)
F(21)-C(54)-C(53)
119.9(3)
F(21)-C(54)-C(55)
118.2(4)
C(53)-C(54)-C(55)
122.0(4)
F(22)-C(55)-C(56)
120.5(4)
F(22)-C(55)-C(54)
120.6(4)
C(56)-C(55)-C(54)
118.9(4)
F(23)-C(56)-C(57)
120.1(4)
F(23)-C(56)-C(55)
119.0(4)
C(57)-C(56)-C(55)
120.9(4)
F(24)-C(57)-C(56)
120.5(4)
F(24)-C(57)-C(58)
120.6(4)
C(56)-C(57)-C(58)
119.0(4)
F(25)-C(58)-C(53)
119.9(3)
F(25)-C(58)-C(57)
117.6(4)
C(53)-C(58)-C(57)
122.5(4)
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table S9. Anisotropic displacement parameters (Å2x 103) for 3. The anisotropic
displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11
U22
U33
U23
U13
U12
______________________________________________________________________________
Mo(1)
18(1)
19(1)
13(1)
0(1)
1(1)
1(1)
C(1)
22(2)
29(2)
11(2)
-2(2)
-2(2)
0(2)
C(2)
27(2)
25(2)
16(2)
1(2)
4(2)
-2(2)
N(1)
26(2)
23(2)
12(2)
-1(1)
1(1)
4(1)
C(11)
24(2)
24(2)
15(2)
1(2)
3(2)
2(2)
C(12)
19(2)
20(2)
18(2)
2(2)
-2(2)
0(2)
C(13)
27(2)
21(2)
23(2)
0(2)
8(2)
0(2)
C(14)
14(2)
24(2)
31(2)
2(2)
7(2)
3(2)
C(15)
29(2)
29(2)
25(2)
5(2)
-3(2)
3(2)
C(16)
33(2)
31(2)
17(2)
1(2)
0(2)
9(2)
F(1)
26(1)
32(1)
15(1)
3(1)
0(1)
8(1)
F(2)
32(1)
42(2)
26(1)
0(1)
13(1)
7(1)
F(3)
23(1)
36(2)
47(2)
3(1)
11(1)
9(1)
F(4)
39(2)
51(2)
31(2)
6(1)
-10(1)
22(1)
F(5)
50(2)
53(2)
14(1)
2(1)
0(1)
22(1)
O(1)
19(1)
19(1)
12(1)
-1(1)
2(1)
0(1)
C(21)
22(2)
24(2)
13(2)
0(2)
3(2)
-4(2)
C(22)
21(2)
23(2)
14(2)
-1(2)
7(2)
-1(2)
C(23)
32(2)
22(2)
28(2)
-4(2)
14(2)
-2(2)
C(24)
38(3)
26(2)
39(3)
-13(2)
13(2)
-10(2)
C(25)
24(2)
37(3)
31(3)
-6(2)
8(2)
-11(2)
C(26)
22(2)
31(2)
17(2)
-4(2)
6(2)
-4(2)
C(27)
23(2)
18(2)
16(2)
-4(2)
9(2)
1(2)
C(28)
31(2)
18(2)
18(2)
-2(2)
9(2)
0(2)
C(29)
29(2)
22(2)
17(2)
1(2)
3(2)
7(2)
C(30)
21(2)
33(3)
25(2)
-7(2)
5(2)
-1(2)
C(31)
25(2)
26(2)
16(2)
-2(2)
7(2)
-7(2)
C(32)
26(2)
21(2)
15(2)
-2(2)
5(2)
1(2)
C(33)
15(2)
31(2)
19(2)
-1(2)
5(2)
-4(2)
C(34)
16(2)
33(2)
20(2)
3(2)
0(2)
-2(2)
C(35)
19(2)
34(2)
20(2)
-7(2)
7(2)
-5(2)
C(36)
16(2)
27(2)
29(2)
-2(2)
7(2)
-2(2)
C(37)
14(2)
35(2)
25(2)
6(2)
-1(2)
-3(2)
C(38)
21(2)
33(2)
13(2)
-3(2)
3(2)
-6(2)
F(6)
38(1)
24(1)
23(1)
6(1)
16(1)
4(1)
F(7)
33(1)
34(2)
26(1)
4(1)
2(1)
11(1)
F(8)
18(1)
52(2)
35(2)
-2(1)
4(1)
-1(1)
F(9)
25(1)
40(2)
30(1)
6(1)
9(1)
-12(1)
F(10)
26(1)
28(1)
18(1)
5(1)
3(1)
0(1)
F(11)
22(1)
49(2)
19(1)
0(1)
0(1)
4(1)
F(12)
24(1)
47(2)
22(1)
-9(1)
5(1)
-2(1)
F(13)
22(1)
35(2)
39(2)
-1(1)
9(1)
6(1)
F(14)
25(1)
47(2)
25(1)
7(1)
-2(1)
4(1)
F(15)
26(1)
51(2)
18(1)
-7(1)
2(1)
-4(1)
O(2)
21(1)
20(1)
14(1)
0(1)
1(1)
-3(1)
C(41)
17(2)
20(2)
15(2)
-4(2)
4(2)
-1(2)
C(42)
21(2)
21(2)
16(2)
0(2)
6(2)
0(2)
C(43)
22(2)
25(2)
13(2)
1(2)
2(2)
-1(2)
C(44)
24(2)
24(2)
20(2)
-5(2)
1(2)
-6(2)
C(45)
22(2)
18(2)
22(2)
-1(2)
5(2)
-1(2)
C(46)
16(2)
23(2)
17(2)
2(2)
4(2)
1(2)
C(47)
24(2)
20(2)
9(2)
-1(1)
2(2)
-1(2)
C(48)
19(2)
26(2)
14(2)
-2(2)
1(2)
-1(2)
C(49)
20(2)
21(2)
19(2)
0(2)
-2(2)
4(2)
C(50)
26(2)
17(2)
17(2)
0(2)
1(2)
-2(2)
C(51)
20(2)
28(2)
10(2)
-1(2)
2(2)
-4(2)
C(52)
23(2)
19(2)
10(2)
0(2)
-2(2)
4(2)
C(53)
22(2)
18(2)
16(2)
2(2)
3(2)
-3(2)
C(54)
21(2)
27(2)
22(2)
3(2)
6(2)
0(2)
C(55)
30(2)
31(2)
12(2)
2(2)
8(2)
1(2)
C(56)
33(2)
20(2)
17(2)
9(2)
-5(2)
-2(2)
C(57)
26(2)
22(2)
25(2)
3(2)
2(2)
7(2)
C(58)
28(2)
24(2)
16(2)
1(2)
5(2)
2(2)
F(16)
18(1)
35(1)
26(1)
6(1)
3(1)
0(1)
F(17)
23(1)
26(1)
33(1)
5(1)
-2(1)
3(1)
F(18)
32(1)
22(1)
28(1)
7(1)
4(1)
-4(1)
F(19)
22(1)
31(1)
23(1)
3(1)
8(1)
-4(1)
F(20)
21(1)
26(1)
20(1)
2(1)
6(1)
4(1)
F(21)
30(1)
64(2)
23(1)
4(1)
10(1)
18(1)
F(22)
42(2)
65(2)
16(1)
5(1)
11(1)
4(1)
F(23)
38(1)
31(1)
22(1)
9(1)
-6(1)
2(1)
F(24)
38(2)
49(2)
34(2)
1(1)
3(1)
23(1)
F(25)
38(2)
45(2)
21(1)
0(1)
10(1)
15(1)
______________________________________________________________________________
Table S10. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for 3.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
H(1A)
7080(30)
6600(5)
9320(50)
26
H(1B)
8138(18)
6346(8)
9500(50)
26
H(2A)
6920(30)
5942(6)
9900(50)
27
H(2B)
5830(20)
6191(9)
9710(50)
27
H(23)
6146
7578
6722
32
H(24)
8140
7659
7357
41
H(25)
9379
7257
7151
37
H(43)
1962
5836
1584
25
H(44)
1791
5350
2652
29
H(45)
3058
5197
5308
25
________________________________________________________________________________
Table S11. Crystal data and structure refinement for 5.
Identification code
12173
Empirical formula
C67 H34 F25 Mo N O6
Formula weight
1519.89
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P1̄
Unit cell dimensions
a = 11.6122(15) Å
= 91.318(2)°.
b = 12.2993(16) Å
= 105.053(2)°.
c = 22.146(3) Å
 = 101.085(2)°.
Volume
2988.6(7) Å3
Z
2
Density (calculated)
1.689 Mg/m3
Absorption coefficient
0.354 mm-1
F(000)
1516
Crystal size
0.34 x 0.26 x 0.21 mm3
Theta range for data collection
1.69 to 30.51°.
Index ranges
-16<=h<=16, -17<=k<=17, -31<=l<=31
Reflections collected
137101
Independent reflections
18222 [Rint = 0.0423]
Completeness to theta = 30.51°
99.8 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.9293 and 0.8878
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
18222 / 542 / 970
Goodness-of-fit on F2
1.053
Final R indices [I>2σ(I)]
R1 = 0.0247, wR2 = 0.0646
R indices (all data)
R1 = 0.0277, wR2 = 0.0668
Largest diff. peak and hole
0.461 and -0.494 e.Å-3
Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103)
for 5. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
C(1)
7237(1)
6309(1)
6714(1)
18(1)
C(2)
8370(1)
6856(1)
6632(1)
19(1)
Mo(1)
7922(1)
7800(1)
7363(1)
11(1)
O(1)
7857(1)
9313(1)
7890(1)
14(1)
O(2)
7732(1)
10982(1)
8244(1)
21(1)
O(3)
6904(1)
8599(1)
6564(1)
15(1)
O(4)
5449(1)
9086(1)
5817(1)
21(1)
C(3)
6108(1)
10116(1)
7433(1)
15(1)
C(4)
5593(1)
9720(1)
6830(1)
14(1)
C(5)
4407(1)
10156(1)
6611(1)
18(1)
C(6)
4787(1)
11430(1)
6622(1)
22(1)
C(7)
5294(1)
11814(1)
7216(1)
22(1)
C(8)
5262(1)
10808(1)
7616(1)
18(1)
C(9)
4027(1)
10082(1)
7234(1)
20(1)
C(10)
7306(1)
10071(1)
7861(1)
14(1)
C(11)
8927(1)
11060(1)
8688(1)
24(1)
C(12)
6055(1)
9083(1)
6412(1)
14(1)
C(13)
5790(1)
8423(1)
5362(1)
27(1)
N(1)
8695(1)
7155(1)
7980(1)
14(1)
C(21)
9394(1)
6728(1)
8478(1)
16(1)
C(22)
10161(1)
7424(1)
8991(1)
18(1)
C(23)
10860(1)
7003(1)
9502(1)
23(1)
C(24)
10807(1)
5871(1)
9502(1)
27(1)
C(25)
10054(1)
5161(1)
9002(1)
28(1)
C(26)
9349(1)
5584(1)
8496(1)
22(1)
F(1)
10212(1)
8517(1)
8989(1)
25(1)
F(2)
11583(1)
7678(1)
9990(1)
33(1)
F(3)
11488(1)
5462(1)
9990(1)
41(1)
F(4)
9999(1)
4065(1)
9017(1)
45(1)
F(5)
8604(1)
4898(1)
8019(1)
33(1)
O(5)
9358(1)
9005(1)
7267(1)
14(1)
C(31)
9967(1)
9126(1)
6834(1)
13(1)
C(32)
10868(1)
8512(1)
6805(1)
15(1)
C(33)
11369(1)
8574(1)
6295(1)
18(1)
C(34)
11050(1)
9275(1)
5825(1)
20(1)
C(35)
10271(1)
9975(1)
5885(1)
18(1)
C(36)
9754(1)
9926(1)
6389(1)
14(1)
C(37)
11361(1)
7868(1)
7336(1)
16(1)
C(38)
11458(1)
6764(1)
7263(1)
20(1)
C(39)
11979(1)
6192(1)
7759(1)
26(1)
C(40)
12476(1)
6736(1)
8348(1)
27(1)
C(41)
12434(1)
7841(1)
8438(1)
23(1)
C(42)
11868(1)
8385(1)
7941(1)
19(1)
C(43)
9090(1)
10794(1)
6499(1)
15(1)
C(44)
8135(1)
11078(1)
6049(1)
17(1)
C(45)
7586(1)
11946(1)
6151(1)
21(1)
C(46)
8003(1)
12588(1)
6715(1)
24(1)
C(47)
8959(1)
12341(1)
7172(1)
23(1)
C(48)
9482(1)
11462(1)
7062(1)
18(1)
F(6)
11030(1)
6206(1)
6693(1)
26(1)
F(7)
11993(1)
5113(1)
7669(1)
38(1)
F(8)
12996(1)
6201(1)
8831(1)
40(1)
F(9)
12944(1)
8382(1)
9006(1)
32(1)
F(10)
11873(1)
9461(1)
8049(1)
23(1)
F(11)
7704(1)
10498(1)
5485(1)
23(1)
F(12)
6648(1)
12161(1)
5706(1)
29(1)
F(13)
7505(1)
13446(1)
6811(1)
34(1)
F(14)
9405(1)
12973(1)
7716(1)
34(1)
F(15)
10450(1)
11306(1)
7509(1)
24(1)
O(6)
6152(1)
7386(1)
7479(1)
13(1)
C(51)
5645(1)
6448(1)
7678(1)
13(1)
C(52)
5850(1)
6322(1)
8332(1)
15(1)
C(53)
5434(1)
5310(1)
8555(1)
20(1)
C(54)
4763(1)
4404(1)
8143(1)
23(1)
C(55)
4464(1)
4541(1)
7507(1)
20(1)
C(56)
4867(1)
5545(1)
7268(1)
15(1)
C(57)
6491(1)
7282(1)
8793(1)
15(1)
C(58)
7480(1)
7216(1)
9295(1)
18(1)
C(59)
8067(1)
8091(1)
9738(1)
22(1)
C(60)
7643(1)
9064(1)
9709(1)
25(1)
C(61)
6638(1)
9156(1)
9231(1)
22(1)
C(62)
6086(1)
8280(1)
8781(1)
17(1)
C(63)
4407(1)
5620(1)
6582(1)
15(1)
C(64)
4447(1)
4799(1)
6146(1)
17(1)
C(65)
3936(1)
4803(1)
5509(1)
19(1)
C(66)
3339(1)
5638(1)
5278(1)
21(1)
C(67)
3294(1)
6480(1)
5693(1)
19(1)
C(68)
3821(1)
6460(1)
6330(1)
16(1)
F(16)
7892(1)
6264(1)
9365(1)
24(1)
F(17)
9051(1)
7991(1)
10194(1)
33(1)
F(18)
8194(1)
9911(1)
10140(1)
39(1)
F(19)
6199(1)
10091(1)
9206(1)
33(1)
F(20)
5099(1)
8406(1)
8333(1)
21(1)
F(21)
5032(1)
3975(1)
6337(1)
23(1)
F(22)
4026(1)
4005(1)
5110(1)
26(1)
F(23)
2823(1)
5634(1)
4664(1)
31(1)
F(24)
2730(1)
7304(1)
5476(1)
27(1)
F(25)
3716(1)
7281(1)
6712(1)
19(1)
C(1S)
5401(2)
6738(1)
10235(1)
40(1)
C(2S)
5229(1)
7771(1)
10412(1)
38(1)
C(3S)
6108(1)
8442(1)
10891(1)
33(1)
C(4S)
7144(1)
8071(1)
11193(1)
31(1)
C(5S)
7308(1)
7039(1)
11018(1)
33(1)
C(6S)
6438(2)
6374(1)
10537(1)
39(1)
C(1T)
1888(4)
2742(3)
6220(2)
38(1)
C(2T)
1156(6)
3480(4)
6292(2)
50(1)
C(3T)
432(5)
3859(4)
5769(3)
61(1)
C(4T)
456(5)
3496(5)
5182(2)
58(1)
C(5T)
1202(4)
2787(4)
5111(1)
46(1)
C(6T)
1912(3)
2409(3)
5627(2)
38(1)
C(1U)
1341(11)
3186(10)
6350(5)
44(2)
C(2U)
479(9)
3751(7)
6051(6)
46(2)
C(3U)
160(8)
3770(7)
5406(6)
51(2)
C(4U)
716(13)
3218(11)
5050(4)
48(2)
C(5U)
1554(9)
2657(7)
5359(7)
45(2)
C(6U)
1890(8)
2644(9)
5998(7)
43(2)
________________________________________________________________________________
Table S13. Bond lengths [Å] and angles [°] for 5.
_____________________________________________________
C(1)-C(2)
1.4161(15)
C(1)-Mo(1)
2.1876(11)
C(1)-H(1A)
0.943(12)
C(1)-H(1B)
0.954(12)
C(2)-Mo(1)
2.1954(11)
C(2)-H(2A)
0.960(12)
C(2)-H(2B)
0.975(12)
Mo(1)-N(1)
1.7290(9)
Mo(1)-O(5)
2.0664(7)
Mo(1)-O(6)
2.1041(7)
Mo(1)-O(1)
2.1983(8)
Mo(1)-O(3)
2.2198(8)
O(1)-C(10)
1.2221(12)
O(2)-C(10)
1.3214(12)
O(2)-C(11)
1.4609(14)
O(3)-C(12)
1.2256(13)
O(4)-C(12)
1.3240(13)
O(4)-C(13)
1.4581(14)
C(3)-C(4)
1.3486(14)
C(3)-C(10)
1.4772(14)
C(3)-C(8)
1.5387(14)
C(4)-C(12)
1.4659(14)
C(4)-C(5)
1.5390(14)
C(5)-C(6)
1.5412(16)
C(5)-C(9)
1.5512(16)
C(5)-H(5)
1.0000
C(6)-C(7)
1.3275(18)
C(6)-H(6)
0.9500
C(7)-C(8)
1.5389(16)
C(7)-H(7)
0.9500
C(8)-C(9)
1.5531(16)
C(8)-H(8)
1.0000
C(9)-H(9A)
0.9900
C(9)-H(9B)
0.9900
C(11)-H(11A)
0.9800
C(11)-H(11B)
0.9800
C(11)-H(11C)
0.9800
C(13)-H(13A)
0.9800
C(13)-H(13B)
0.9800
C(13)-H(13C)
0.9800
N(1)-C(21)
1.3698(13)
C(21)-C(22)
1.3982(16)
C(21)-C(26)
1.3995(15)
C(22)-F(1)
1.3345(13)
C(22)-C(23)
1.3843(15)
C(23)-F(2)
1.3355(15)
C(23)-C(24)
1.3825(18)
C(24)-F(3)
1.3341(14)
C(24)-C(25)
1.383(2)
C(25)-F(4)
1.3386(14)
C(25)-C(26)
1.3820(17)
C(26)-F(5)
1.3345(15)
O(5)-C(31)
1.3248(12)
C(31)-C(32)
1.4158(14)
C(31)-C(36)
C(32)-C(33)
C(32)-C(37)
C(33)-C(34)
C(33)-H(33)
C(34)-C(35)
C(34)-H(34)
C(35)-C(36)
C(35)-H(35)
C(36)-C(43)
C(37)-C(38)
C(37)-C(42)
C(38)-F(6)
C(38)-C(39)
C(39)-F(7)
C(39)-C(40)
C(40)-F(8)
C(40)-C(41)
C(41)-F(9)
C(41)-C(42)
C(42)-F(10)
C(43)-C(44)
C(43)-C(48)
C(44)-F(11)
C(44)-C(45)
C(45)-F(12)
C(45)-C(46)
C(46)-F(13)
C(46)-C(47)
C(47)-F(14)
C(47)-C(48)
C(48)-F(15)
O(6)-C(51)
C(51)-C(56)
C(51)-C(52)
C(52)-C(53)
C(52)-C(57)
C(53)-C(54)
C(53)-H(53)
C(54)-C(55)
C(54)-H(54)
C(55)-C(56)
C(55)-H(55)
C(56)-C(63)
C(57)-C(58)
C(57)-C(62)
C(58)-F(16)
C(58)-C(59)
C(59)-F(17)
C(59)-C(60)
C(60)-F(18)
C(60)-C(61)
C(61)-F(19)
C(61)-C(62)
C(62)-F(20)
C(63)-C(68)
1.4192(14)
1.3972(14)
1.4842(15)
1.3884(16)
0.9500
1.3912(16)
0.9500
1.3964(14)
0.9500
1.4816(15)
1.3935(15)
1.3970(16)
1.3475(14)
1.3864(17)
1.3414(15)
1.378(2)
1.3388(14)
1.3822(19)
1.3409(15)
1.3847(16)
1.3378(13)
1.3913(15)
1.3966(15)
1.3479(13)
1.3867(16)
1.3394(13)
1.3810(18)
1.3348(13)
1.3822(17)
1.3424(14)
1.3827(16)
1.3398(13)
1.3299(12)
1.4199(14)
1.4213(14)
1.3959(15)
1.4846(15)
1.3895(17)
0.9500
1.3832(17)
0.9500
1.4011(15)
0.9500
1.4861(15)
1.3924(15)
1.3949(15)
1.3449(13)
1.3813(17)
1.3420(13)
1.3758(19)
1.3361(14)
1.3821(18)
1.3414(14)
1.3844(16)
1.3440(12)
1.3929(15)
C(63)-C(64)
C(64)-F(21)
C(64)-C(65)
C(65)-F(22)
C(65)-C(66)
C(66)-F(23)
C(66)-C(67)
C(67)-F(24)
C(67)-C(68)
C(68)-F(25)
C(1S)-C(6S)
C(1S)-C(2S)
C(1S)-H(1S)
C(2S)-C(3S)
C(2S)-H(2S)
C(3S)-C(4S)
C(3S)-H(3S)
C(4S)-C(5S)
C(4S)-H(4S)
C(5S)-C(6S)
C(5S)-H(5S)
C(6S)-H(6S)
C(1T)-C(6T)
C(1T)-C(2T)
C(1T)-H(1T)
C(2T)-C(3T)
C(2T)-H(2T)
C(3T)-C(4T)
C(3T)-H(3T)
C(4T)-C(5T)
C(4T)-H(4T)
C(5T)-C(6T)
C(5T)-H(5T)
C(6T)-H(6T)
C(1U)-C(6U)
C(1U)-C(2U)
C(1U)-H(1U)
C(2U)-C(3U)
C(2U)-H(2U)
C(3U)-C(4U)
C(3U)-H(3U)
C(4U)-C(5U)
C(4U)-H(4U)
C(5U)-C(6U)
C(5U)-H(5U)
C(6U)-H(6U)
C(2)-C(1)-Mo(1)
C(2)-C(1)-H(1A)
Mo(1)-C(1)-H(1A)
C(2)-C(1)-H(1B)
Mo(1)-C(1)-H(1B)
H(1A)-C(1)-H(1B)
C(1)-C(2)-Mo(1)
C(1)-C(2)-H(2A)
Mo(1)-C(2)-H(2A)
1.3971(14)
1.3419(13)
1.3818(16)
1.3431(12)
1.3816(17)
1.3359(13)
1.3866(16)
1.3416(13)
1.3868(15)
1.3472(12)
1.378(3)
1.387(2)
0.9500
1.386(2)
0.9500
1.382(2)
0.9500
1.381(2)
0.9500
1.382(2)
0.9500
0.9500
1.375(4)
1.390(5)
0.9500
1.390(6)
0.9500
1.374(6)
0.9500
1.374(6)
0.9500
1.373(4)
0.9500
0.9500
1.363(10)
1.367(10)
0.9500
1.382(10)
0.9500
1.379(10)
0.9500
1.351(10)
0.9500
1.368(10)
0.9500
0.9500
71.45(6)
118.7(9)
108.1(9)
118.9(9)
112.6(9)
116.9(13)
70.85(6)
120.4(9)
108.1(9)
C(1)-C(2)-H(2B)
Mo(1)-C(2)-H(2B)
H(2A)-C(2)-H(2B)
N(1)-Mo(1)-O(5)
N(1)-Mo(1)-O(6)
O(5)-Mo(1)-O(6)
N(1)-Mo(1)-C(1)
O(5)-Mo(1)-C(1)
O(6)-Mo(1)-C(1)
N(1)-Mo(1)-C(2)
O(5)-Mo(1)-C(2)
O(6)-Mo(1)-C(2)
C(1)-Mo(1)-C(2)
N(1)-Mo(1)-O(1)
O(5)-Mo(1)-O(1)
O(6)-Mo(1)-O(1)
C(1)-Mo(1)-O(1)
C(2)-Mo(1)-O(1)
N(1)-Mo(1)-O(3)
O(5)-Mo(1)-O(3)
O(6)-Mo(1)-O(3)
C(1)-Mo(1)-O(3)
C(2)-Mo(1)-O(3)
O(1)-Mo(1)-O(3)
C(10)-O(1)-Mo(1)
C(10)-O(2)-C(11)
C(12)-O(3)-Mo(1)
C(12)-O(4)-C(13)
C(4)-C(3)-C(10)
C(4)-C(3)-C(8)
C(10)-C(3)-C(8)
C(3)-C(4)-C(12)
C(3)-C(4)-C(5)
C(12)-C(4)-C(5)
C(4)-C(5)-C(6)
C(4)-C(5)-C(9)
C(6)-C(5)-C(9)
C(4)-C(5)-H(5)
C(6)-C(5)-H(5)
C(9)-C(5)-H(5)
C(7)-C(6)-C(5)
C(7)-C(6)-H(6)
C(5)-C(6)-H(6)
C(6)-C(7)-C(8)
C(6)-C(7)-H(7)
C(8)-C(7)-H(7)
C(3)-C(8)-C(7)
C(3)-C(8)-C(9)
C(7)-C(8)-C(9)
C(3)-C(8)-H(8)
C(7)-C(8)-H(8)
C(9)-C(8)-H(8)
C(5)-C(9)-C(8)
C(5)-C(9)-H(9A)
C(8)-C(9)-H(9A)
C(5)-C(9)-H(9B)
119.0(9)
113.3(9)
115.3(13)
99.06(4)
99.87(4)
148.94(3)
95.73(4)
120.68(4)
81.53(3)
95.21(4)
83.75(4)
118.59(4)
37.70(4)
98.52(4)
73.81(3)
79.21(3)
157.71(4)
155.23(4)
178.92(4)
81.91(3)
79.44(3)
83.35(4)
84.41(4)
82.20(3)
142.12(7)
116.49(9)
142.03(7)
116.46(9)
131.05(9)
107.01(9)
121.58(9)
129.76(9)
106.87(9)
123.15(9)
106.42(9)
97.95(8)
98.89(9)
116.9
116.9
116.9
107.41(10)
126.3
126.3
107.26(10)
126.4
126.4
106.22(9)
97.98(8)
99.07(9)
116.9
116.9
116.9
92.66(8)
113.2
113.2
113.2
C(8)-C(9)-H(9B)
H(9A)-C(9)-H(9B)
O(1)-C(10)-O(2)
O(1)-C(10)-C(3)
O(2)-C(10)-C(3)
O(2)-C(11)-H(11A)
O(2)-C(11)-H(11B)
H(11A)-C(11)-H(11B)
O(2)-C(11)-H(11C)
H(11A)-C(11)-H(11C)
H(11B)-C(11)-H(11C)
O(3)-C(12)-O(4)
O(3)-C(12)-C(4)
O(4)-C(12)-C(4)
O(4)-C(13)-H(13A)
O(4)-C(13)-H(13B)
H(13A)-C(13)-H(13B)
O(4)-C(13)-H(13C)
H(13A)-C(13)-H(13C)
H(13B)-C(13)-H(13C)
C(21)-N(1)-Mo(1)
N(1)-C(21)-C(22)
N(1)-C(21)-C(26)
C(22)-C(21)-C(26)
F(1)-C(22)-C(23)
F(1)-C(22)-C(21)
C(23)-C(22)-C(21)
F(2)-C(23)-C(24)
F(2)-C(23)-C(22)
C(24)-C(23)-C(22)
F(3)-C(24)-C(23)
F(3)-C(24)-C(25)
C(23)-C(24)-C(25)
F(4)-C(25)-C(26)
F(4)-C(25)-C(24)
C(26)-C(25)-C(24)
F(5)-C(26)-C(25)
F(5)-C(26)-C(21)
C(25)-C(26)-C(21)
C(31)-O(5)-Mo(1)
O(5)-C(31)-C(32)
O(5)-C(31)-C(36)
C(32)-C(31)-C(36)
C(33)-C(32)-C(31)
C(33)-C(32)-C(37)
C(31)-C(32)-C(37)
C(34)-C(33)-C(32)
C(34)-C(33)-H(33)
C(32)-C(33)-H(33)
C(33)-C(34)-C(35)
C(33)-C(34)-H(34)
C(35)-C(34)-H(34)
C(34)-C(35)-C(36)
C(34)-C(35)-H(35)
C(36)-C(35)-H(35)
C(35)-C(36)-C(31)
113.2
110.5
121.97(9)
127.47(9)
110.54(9)
109.5
109.5
109.5
109.5
109.5
109.5
121.27(10)
126.79(9)
111.94(9)
109.5
109.5
109.5
109.5
109.5
109.5
174.71(8)
120.83(9)
121.39(10)
117.77(10)
119.44(10)
119.07(9)
121.49(10)
119.92(11)
120.75(11)
119.34(12)
119.57(13)
119.93(12)
120.51(11)
120.51(13)
119.56(12)
119.92(11)
119.96(11)
119.06(10)
120.97(12)
132.22(6)
122.80(9)
119.77(9)
117.39(9)
120.08(10)
119.04(9)
120.71(9)
121.32(10)
119.3
119.3
119.03(10)
120.5
120.5
120.64(10)
119.7
119.7
120.64(10)
C(35)-C(36)-C(43)
C(31)-C(36)-C(43)
C(38)-C(37)-C(42)
C(38)-C(37)-C(32)
C(42)-C(37)-C(32)
F(6)-C(38)-C(39)
F(6)-C(38)-C(37)
C(39)-C(38)-C(37)
F(7)-C(39)-C(40)
F(7)-C(39)-C(38)
C(40)-C(39)-C(38)
F(8)-C(40)-C(39)
F(8)-C(40)-C(41)
C(39)-C(40)-C(41)
F(9)-C(41)-C(40)
F(9)-C(41)-C(42)
C(40)-C(41)-C(42)
F(10)-C(42)-C(41)
F(10)-C(42)-C(37)
C(41)-C(42)-C(37)
C(44)-C(43)-C(48)
C(44)-C(43)-C(36)
C(48)-C(43)-C(36)
F(11)-C(44)-C(45)
F(11)-C(44)-C(43)
C(45)-C(44)-C(43)
F(12)-C(45)-C(46)
F(12)-C(45)-C(44)
C(46)-C(45)-C(44)
F(13)-C(46)-C(45)
F(13)-C(46)-C(47)
C(45)-C(46)-C(47)
F(14)-C(47)-C(46)
F(14)-C(47)-C(48)
C(46)-C(47)-C(48)
F(15)-C(48)-C(47)
F(15)-C(48)-C(43)
C(47)-C(48)-C(43)
C(51)-O(6)-Mo(1)
O(6)-C(51)-C(56)
O(6)-C(51)-C(52)
C(56)-C(51)-C(52)
C(53)-C(52)-C(51)
C(53)-C(52)-C(57)
C(51)-C(52)-C(57)
C(54)-C(53)-C(52)
C(54)-C(53)-H(53)
C(52)-C(53)-H(53)
C(55)-C(54)-C(53)
C(55)-C(54)-H(54)
C(53)-C(54)-H(54)
C(54)-C(55)-C(56)
C(54)-C(55)-H(55)
C(56)-C(55)-H(55)
C(55)-C(56)-C(51)
C(55)-C(56)-C(63)
119.57(9)
119.46(9)
115.66(10)
123.47(10)
120.61(10)
117.24(11)
120.01(10)
122.75(11)
120.04(12)
120.26(12)
119.70(11)
120.57(12)
119.96(13)
119.47(11)
119.72(11)
120.41(12)
119.87(12)
117.55(10)
119.88(10)
122.48(11)
115.28(10)
124.14(10)
120.31(9)
117.17(10)
119.96(10)
122.87(10)
119.90(11)
120.12(11)
119.99(10)
120.50(11)
120.53(12)
118.95(11)
120.07(11)
119.89(11)
120.01(11)
117.13(10)
119.86(10)
122.88(10)
127.08(6)
123.32(9)
120.07(9)
116.59(9)
121.32(10)
118.45(10)
120.22(9)
120.86(11)
119.6
119.6
118.55(10)
120.7
120.7
121.91(10)
119.0
119.0
120.23(10)
116.92(9)
C(51)-C(56)-C(63)
C(58)-C(57)-C(62)
C(58)-C(57)-C(52)
C(62)-C(57)-C(52)
F(16)-C(58)-C(59)
F(16)-C(58)-C(57)
C(59)-C(58)-C(57)
F(17)-C(59)-C(60)
F(17)-C(59)-C(58)
C(60)-C(59)-C(58)
F(18)-C(60)-C(59)
F(18)-C(60)-C(61)
C(59)-C(60)-C(61)
F(19)-C(61)-C(60)
F(19)-C(61)-C(62)
C(60)-C(61)-C(62)
F(20)-C(62)-C(61)
F(20)-C(62)-C(57)
C(61)-C(62)-C(57)
C(68)-C(63)-C(64)
C(68)-C(63)-C(56)
C(64)-C(63)-C(56)
F(21)-C(64)-C(65)
F(21)-C(64)-C(63)
C(65)-C(64)-C(63)
F(22)-C(65)-C(66)
F(22)-C(65)-C(64)
C(66)-C(65)-C(64)
F(23)-C(66)-C(65)
F(23)-C(66)-C(67)
C(65)-C(66)-C(67)
F(24)-C(67)-C(66)
F(24)-C(67)-C(68)
C(66)-C(67)-C(68)
F(25)-C(68)-C(67)
F(25)-C(68)-C(63)
C(67)-C(68)-C(63)
C(6S)-C(1S)-C(2S)
C(6S)-C(1S)-H(1S)
C(2S)-C(1S)-H(1S)
C(3S)-C(2S)-C(1S)
C(3S)-C(2S)-H(2S)
C(1S)-C(2S)-H(2S)
C(4S)-C(3S)-C(2S)
C(4S)-C(3S)-H(3S)
C(2S)-C(3S)-H(3S)
C(5S)-C(4S)-C(3S)
C(5S)-C(4S)-H(4S)
C(3S)-C(4S)-H(4S)
C(4S)-C(5S)-C(6S)
C(4S)-C(5S)-H(5S)
C(6S)-C(5S)-H(5S)
C(1S)-C(6S)-C(5S)
C(1S)-C(6S)-H(6S)
C(5S)-C(6S)-H(6S)
C(6T)-C(1T)-C(2T)
122.81(9)
115.47(10)
122.08(10)
122.27(9)
117.36(10)
119.75(10)
122.89(11)
120.20(11)
119.96(11)
119.84(11)
120.35(12)
120.31(12)
119.34(11)
119.87(11)
120.31(11)
119.82(11)
117.33(10)
120.07(10)
122.57(10)
115.32(10)
122.64(9)
121.86(10)
117.00(10)
120.08(10)
122.89(10)
119.57(11)
120.33(10)
120.09(10)
120.28(10)
120.77(11)
118.95(11)
119.80(10)
120.39(10)
119.81(10)
117.20(9)
119.85(9)
122.92(10)
120.18(14)
119.9
119.9
119.81(15)
120.1
120.1
119.71(14)
120.1
120.1
120.33(13)
119.8
119.8
119.99(14)
120.0
120.0
119.99(14)
120.0
120.0
119.4(4)
C(6T)-C(1T)-H(1T)
120.3
C(2T)-C(1T)-H(1T)
120.3
C(1T)-C(2T)-C(3T)
120.4(4)
C(1T)-C(2T)-H(2T)
119.8
C(3T)-C(2T)-H(2T)
119.8
C(4T)-C(3T)-C(2T)
119.0(4)
C(4T)-C(3T)-H(3T)
120.5
C(2T)-C(3T)-H(3T)
120.5
C(3T)-C(4T)-C(5T)
120.6(4)
C(3T)-C(4T)-H(4T)
119.7
C(5T)-C(4T)-H(4T)
119.7
C(6T)-C(5T)-C(4T)
120.3(3)
C(6T)-C(5T)-H(5T)
119.8
C(4T)-C(5T)-H(5T)
119.8
C(5T)-C(6T)-C(1T)
120.2(3)
C(5T)-C(6T)-H(6T)
119.9
C(1T)-C(6T)-H(6T)
119.9
C(6U)-C(1U)-C(2U)
118.5(9)
C(6U)-C(1U)-H(1U)
120.8
C(2U)-C(1U)-H(1U)
120.8
C(1U)-C(2U)-C(3U)
121.1(8)
C(1U)-C(2U)-H(2U)
119.4
C(3U)-C(2U)-H(2U)
119.4
C(4U)-C(3U)-C(2U)
120.3(9)
C(4U)-C(3U)-H(3U)
119.9
C(2U)-C(3U)-H(3U)
119.9
C(5U)-C(4U)-C(3U)
117.3(8)
C(5U)-C(4U)-H(4U)
121.4
C(3U)-C(4U)-H(4U)
121.4
C(4U)-C(5U)-C(6U)
123.0(7)
C(4U)-C(5U)-H(5U)
118.5
C(6U)-C(5U)-H(5U)
118.5
C(1U)-C(6U)-C(5U)
119.8(8)
C(1U)-C(6U)-H(6U)
120.1
C(5U)-C(6U)-H(6U)
120.1
_____________________________________________________________
Symmetry transformations used to generate equivalent atoms:
Table S14. Anisotropic displacement parameters (Å2x 103) for 5. The anisotropic
displacement factor exponent takes the form: -22[ h2 a*2U11 + ... + 2 h k a* b* U12 ]
______________________________________________________________________________
U11
U22
U33
U23
U13
U12
______________________________________________________________________________
C(1)
15(1)
15(1)
22(1)
-5(1)
7(1)
1(1)
C(2)
15(1)
19(1)
23(1)
-7(1)
8(1)
1(1)
Mo(1)
10(1)
10(1)
12(1)
0(1)
3(1)
2(1)
O(1)
14(1)
14(1)
14(1)
0(1)
4(1)
3(1)
O(2)
21(1)
17(1)
20(1)
-6(1)
-2(1)
6(1)
O(3)
15(1)
16(1)
14(1)
2(1)
4(1)
4(1)
O(4)
20(1)
28(1)
13(1)
-3(1)
-1(1)
8(1)
C(3)
14(1)
14(1)
17(1)
1(1)
5(1)
4(1)
C(4)
12(1)
13(1)
16(1)
2(1)
3(1)
3(1)
C(5)
13(1)
20(1)
20(1)
2(1)
3(1)
6(1)
C(6)
21(1)
19(1)
28(1)
7(1)
7(1)
10(1)
C(7)
22(1)
16(1)
32(1)
2(1)
8(1)
9(1)
C(8)
17(1)
20(1)
20(1)
-1(1)
6(1)
8(1)
C(9)
15(1)
24(1)
24(1)
3(1)
7(1)
6(1)
C(10)
14(1)
14(1)
13(1)
0(1)
4(1)
2(1)
C(11)
22(1)
22(1)
21(1)
-5(1)
-5(1)
3(1)
C(12)
13(1)
12(1)
14(1)
0(1)
2(1)
0(1)
C(13)
27(1)
35(1)
17(1)
-9(1)
2(1)
6(1)
N(1)
14(1)
12(1)
17(1)
1(1)
5(1)
4(1)
C(21)
16(1)
15(1)
19(1)
5(1)
7(1)
6(1)
C(22)
18(1)
17(1)
20(1)
6(1)
5(1)
5(1)
C(23)
20(1)
29(1)
19(1)
6(1)
4(1)
7(1)
C(24)
32(1)
33(1)
24(1)
14(1)
9(1)
20(1)
C(25)
42(1)
21(1)
31(1)
11(1)
14(1)
20(1)
C(26)
31(1)
17(1)
23(1)
3(1)
9(1)
11(1)
F(1)
28(1)
15(1)
26(1)
2(1)
-2(1)
2(1)
F(2)
30(1)
40(1)
22(1)
5(1)
-4(1)
6(1)
F(3)
51(1)
48(1)
30(1)
21(1)
6(1)
31(1)
F(4)
78(1)
23(1)
42(1)
12(1)
13(1)
30(1)
F(5)
52(1)
16(1)
30(1)
-2(1)
5(1)
10(1)
O(5)
14(1)
13(1)
15(1)
1(1)
6(1)
2(1)
C(31)
12(1)
13(1)
14(1)
0(1)
4(1)
0(1)
C(32)
12(1)
15(1)
16(1)
0(1)
4(1)
2(1)
C(33)
13(1)
23(1)
18(1)
-1(1)
6(1)
4(1)
C(34)
16(1)
29(1)
16(1)
1(1)
7(1)
4(1)
C(35)
16(1)
22(1)
14(1)
2(1)
4(1)
1(1)
C(36)
13(1)
15(1)
14(1)
0(1)
3(1)
1(1)
C(37)
11(1)
18(1)
20(1)
3(1)
6(1)
4(1)
C(38)
16(1)
21(1)
26(1)
2(1)
8(1)
7(1)
C(39)
22(1)
23(1)
39(1)
10(1)
14(1)
13(1)
C(40)
20(1)
38(1)
30(1)
17(1)
10(1)
15(1)
C(41)
16(1)
35(1)
20(1)
6(1)
5(1)
5(1)
C(42)
14(1)
22(1)
20(1)
3(1)
5(1)
3(1)
C(43)
15(1)
14(1)
16(1)
3(1)
4(1)
2(1)
C(44)
16(1)
18(1)
16(1)
3(1)
3(1)
1(1)
C(45)
18(1)
22(1)
24(1)
9(1)
4(1)
6(1)
C(46)
26(1)
17(1)
31(1)
5(1)
9(1)
9(1)
C(47)
29(1)
17(1)
23(1)
-2(1)
4(1)
6(1)
C(48)
20(1)
16(1)
18(1)
1(1)
2(1)
5(1)
F(6)
25(1)
22(1)
32(1)
-5(1)
7(1)
8(1)
F(7)
42(1)
26(1)
56(1)
13(1)
18(1)
22(1)
F(8)
36(1)
55(1)
38(1)
27(1)
12(1)
28(1)
F(9)
27(1)
49(1)
18(1)
5(1)
1(1)
7(1)
F(10)
25(1)
21(1)
20(1)
-2(1)
3(1)
2(1)
F(11)
21(1)
29(1)
16(1)
0(1)
1(1)
4(1)
F(12)
24(1)
34(1)
31(1)
12(1)
1(1)
14(1)
F(13)
38(1)
23(1)
45(1)
3(1)
11(1)
18(1)
F(14)
45(1)
25(1)
30(1)
-11(1)
1(1)
14(1)
F(15)
25(1)
22(1)
20(1)
-3(1)
-4(1)
8(1)
O(6)
12(1)
12(1)
16(1)
2(1)
6(1)
2(1)
C(51)
12(1)
12(1)
16(1)
2(1)
6(1)
3(1)
C(52)
16(1)
15(1)
17(1)
1(1)
6(1)
3(1)
C(53)
25(1)
18(1)
20(1)
5(1)
11(1)
3(1)
C(54)
28(1)
15(1)
28(1)
4(1)
13(1)
0(1)
C(55)
20(1)
14(1)
25(1)
-1(1)
8(1)
-1(1)
C(56)
14(1)
14(1)
19(1)
0(1)
6(1)
2(1)
C(57)
15(1)
16(1)
13(1)
3(1)
5(1)
3(1)
C(58)
17(1)
22(1)
17(1)
6(1)
6(1)
6(1)
C(59)
18(1)
32(1)
15(1)
4(1)
1(1)
1(1)
C(60)
29(1)
24(1)
17(1)
-3(1)
4(1)
-4(1)
C(61)
30(1)
17(1)
20(1)
1(1)
9(1)
4(1)
C(62)
18(1)
18(1)
14(1)
2(1)
4(1)
4(1)
C(63)
11(1)
14(1)
19(1)
-2(1)
5(1)
0(1)
C(64)
15(1)
12(1)
24(1)
-1(1)
7(1)
1(1)
C(65)
20(1)
15(1)
22(1)
-6(1)
10(1)
-1(1)
C(66)
22(1)
22(1)
17(1)
-2(1)
5(1)
1(1)
C(67)
18(1)
20(1)
20(1)
0(1)
5(1)
6(1)
C(68)
13(1)
16(1)
18(1)
-3(1)
5(1)
2(1)
F(16)
24(1)
28(1)
24(1)
11(1)
9(1)
14(1)
F(17)
21(1)
51(1)
20(1)
5(1)
-4(1)
3(1)
F(18)
50(1)
30(1)
24(1)
-10(1)
1(1)
-9(1)
F(19)
51(1)
19(1)
30(1)
-2(1)
10(1)
14(1)
F(20)
21(1)
25(1)
19(1)
3(1)
3(1)
11(1)
F(21)
26(1)
15(1)
30(1)
-1(1)
8(1)
8(1)
F(22)
35(1)
19(1)
26(1)
-9(1)
13(1)
2(1)
F(23)
43(1)
32(1)
16(1)
-2(1)
4(1)
8(1)
F(24)
34(1)
30(1)
21(1)
2(1)
4(1)
18(1)
F(25)
20(1)
20(1)
20(1)
-5(1)
4(1)
9(1)
C(1S)
44(1)
43(1)
24(1)
-6(1)
10(1)
-15(1)
C(2S)
28(1)
50(1)
31(1)
6(1)
3(1)
4(1)
C(3S)
34(1)
31(1)
34(1)
-1(1)
8(1)
8(1)
C(4S)
28(1)
33(1)
26(1)
-1(1)
3(1)
1(1)
C(5S)
36(1)
35(1)
35(1)
11(1)
17(1)
12(1)
C(6S)
60(1)
25(1)
38(1)
2(1)
31(1)
1(1)
C(1T)
42(2)
31(1)
28(1)
-2(1)
2(1)
-16(1)
C(2T)
57(3)
38(2)
47(2)
-14(2)
19(2)
-12(2)
C(3T)
50(2)
43(2)
83(4)
-4(2)
10(2)
1(1)
C(4T)
48(3)
47(3)
57(3)
10(2)
-12(2)
-8(2)
C(5T)
47(2)
49(2)
26(1)
3(1)
6(1)
-20(2)
C(6T)
30(1)
34(1)
44(2)
-3(1)
11(1)
-10(1)
C(1U)
37(4)
43(6)
38(3)
1(3)
9(2)
-22(3)
C(2U)
34(3)
31(3)
72(5)
-12(4)
27(4)
-10(2)
C(3U)
35(4)
28(3)
76(6)
-3(4)
0(4)
-6(2)
C(4U)
50(6)
42(6)
34(3)
-2(3)
-1(3)
-14(3)
C(5U)
40(5)
36(4)
59(5)
-9(4)
24(4)
-2(3)
C(6U)
26(3)
37(4)
62(5)
7(5)
6(4)
1(2)
______________________________________________________________________________
Table S15. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 10 3)
for 5.
________________________________________________________________________________
x
y
z
U(eq)
________________________________________________________________________________
H(1A)
6514(12)
6398(12)
6423(7)
21
H(1B)
7201(14)
5640(11)
6925(7)
21
H(2A)
8397(14)
7316(12)
6289(6)
23
H(2B)
9086(12)
6536(13)
6790(7)
23
H(5)
3793
9767
6226
21
H(6)
4679
11860
6268
26
H(7)
5618
12570
7366
27
H(8)
5367
10963
8074
22
H(9A)
3883
9316
7366
24
H(9B)
3322
10428
7228
24
H(11A)
8868
10506
8995
36
H(11B)
9202
11806
8905
36
H(11C)
9511
10922
8461
36
H(13A)
6680
8556
5455
41
H(13B)
5451
8635
4939
41
H(13C)
5467
7634
5388
41
H(33)
11940
8127
6269
21
H(34)
11360
9276
5468
24
H(35)
10089
10492
5579
21
H(53)
5611
5240
8994
25
H(54)
4515
3706
8295
28
H(55)
3971
3936
7224
24
H(1S)
4803
6279
9904
49
H(2S)
4511
8018
10205
46
H(3S)
5998
9153
11011
40
H(4S)
7747
8529
11522
37
H(5S)
8020
6786
11229
40
H(6S)
6554
5666
10415
46
H(1T)
2367
2471
6578
46
H(2T)
1150
3728
6700
60
H(3T)
-72
4360
5817
73
H(4T)
-48
3737
4822
69
H(5T)
1227
2559
4703
55
H(6T)
2421
1916
5575
46
H(1U)
1552
3171
6794
52
H(2U)
93
4138
6290
55
H(3U)
-444
4164
5206
62
H(4U)
517
3232
4607
57
H(5U)
1928
2252
5121
54
H(6U)
2504
2259
6195
52
________________________________________________________________________________
References
1
2
3
Sheldrick, G. M., Acta Cryst. 1990, A46, 467-473.
Sheldrick, G. M., Acta Cryst. 2008, A64, 112-122.
Müller, P. Crystallography Reviews 2009, 15, 57-83.