This journal is © The Owner Societies 1999
Table S1a. Selected bond distances (Å) and angles () and v(MO) IR stretching frequencies (cm-1) for Re(V)
oxo- and dioxo-complexes.
--------------------------------------------------------------------------------------------------------------------------------------Compound
trans-ligand d(MO)
d(M-O)
<α>
v(MO) Ref.
--------------------------------------------------------------------------------------------------------------------------------------[ReO2(cyclam)]+
O21.775(9)
1.775(9)
90.0
a
[ReO2(cyclam)]+
O2-
1.78(1)
1.78(1)
90.4
776
b
[ReO2(en)2]+
O2-
1.761(7)
1.769(7)
90.6
814
c
[ReO2(py)4]+
O2-
1.74(1)
1.78(1)
90.7
814
c
[ReO2(cyclam)]+
O2-
1.756(3)
1.756(3)
90.0
825
d
ReOCl2(OEt)(py)2
EtO-
1.684(7)
1.896(6)
91.9
-
e
[ReO(OEt)(PNH)2] (β-form)
EtO-
1.717(8)
1.997(8)
95.9
885
f
[ReO(OEt)(PNH)2] (α-form)
EtO-
1.692(7)
2.004(7)
96.3
887
g
ReOI2(OEt)(PPh3)2
EtO-
1.715(9)
1.880(9)
92.2
945
h
[ReO(OEt){N(SPPh2)2}2]
EtO-
1.70(1)
1.90(1)
90.3
950
i
[ReO(OEt)(Ph2PNPPh2Se)2]
EtO-
1.70(2)
1.86(2)
90.5
950
j
ReOCl2(OEt)(PPh3)2
EtO-
1.699(4)
1.888( 4)
91.6
955
k
[ReCl2O(OEt)(Haza)PPh3]
EtO-
1.691(6)
1.885(6)
91.8
--
l
[ReOCl2(OC3H7)(PPh3)2]
PropO-
1.698(2)
1.890(2)
90.3
--
m
[ReO(OH)(Ocyclam)]+
OH-
1.685(8)
1.970(8)
94.9
952
n
[ReO(OH)(CN)4]2-
OH-
1.70(1)
1.90(1)
92.3
--
o
ReOI2(OMe)(PPh3)2
MeO-
1.698(5)
1.859(5)
92.6
930
h
[ReO(OMe)(dppd)]
MeO -
1.699(8)
2.011(9)
98.2
915
p
[ReO(acac)(η2-B(pz)4)OMe]
MeO-
1.681(5)
1.896(5)
93.1
955
q
[ReO(OMe)L]
MeO -
1.679(7)
1.875(6)
92.6
--
r
[cis-(P,P)-ReO(PO)(PO)2]
ArO-
1.692(3)
2.050(3)
97.6
965
s
[ReOCl(PO2)]
Ar-O-
1.69(1)
2.032(9)
97.7
959
t
[ReOCl(PO)(PNH)]
Ar-O-
1.70(1)
2.04(1)
97.5
941
t
[ReOBr(oz)2]
Ar-O-
1.681(4)
1.988(4)
970
u
[ReOCl2 (salampH)]
Ar-O-
1.680(7)
1.943(7)
94.9
92.4
978
v
This journal is © The Owner Societies 1999
Table S1a. Cont.
[ReOCl2 (salimp)]
[ReOClL’2]
Ar-O-
1.695(9)
1.953(9)
92.6
--
v
ArO -
1.688(6)
1.977(5)
94.7
--
w
trans-ReOCl2(PPh3)(Me-sal) Ar-O-
1.701(5)
1.949(5)
94.7
--
x
Ar-O-
1.680(4)
1.979(4)
95.1
962
y
trans-ReOBr2(PPh3)(Ph-sal) Ar-O-
1.683(5)
1.937(5)
93.9
965
z
cis-ReOCl2(PPh3)(Me-sal)
Ar-O-
1.660(8)
1.955(6)
94.0
967
x
Re2CL4O2(PPh3)2(salen)2
Ar-O-
1.68(1)
1.68(1)
93.1
92.7
969
aa
trans-ReOBr2(PPh3)(Ph-sal)
(triclinic form)
Ar-O-
1.680(4)
1.972(4)
95.1
973
ab
[ReOClL'']
ArO -
1.679(5)
1.994(5)
95.6
952
ac
[ReOClL''']
ArO -
1.680(3)
1.981(3)
94.5
957
ac
[ReO(PPh3)(cat)2]-
ArO-
1.693(8)
2.041(7)
92.6
941
ad
[ReOBr3(ma)]-
Ar-O-
1.664(5)
2.103(5)
95.4
970
ae
[ReOBr(ma)2]
Ar-O-
1.673(8)
2.028(7)
97.3
975
ae
ReOCl2(acac)(PPh3)
acac-
1.69(1)
2.10(1)
97.0
--
af
[ReO(O2CCF3)(dppd)]
CF3COO-
1.682(6)
2.174(6)
98.5
892
p
[ReO(H2O)Cl2tu2]+
H2O
1.65(1)
2.23(1)
98.3
--
ag
[ReO(H2O)Cl4]-
H2O
1.660(9)
2.20(1)
97.7
--
ah
[ReO(H2O)(CN)4]-
H2O
1.667(8)
2.142(7)
98.4
--
ai
ReOCl2(PPh3)(Acbhyz)
RO-
1.685(8)
2.013(7)
95.9
--
[ReOCl2{N(OPPh2)2}(PPh3)]
RO-
1.660(5)
2.071(4)
95.9
960
i
[ReOCl2(OPPh2CH2PPh2)]
RO-
1.688(9)
1.694(9)
2.137(9)
96.9
2.146(9)
97.1
965
ak
[ReOCl(Me-sal)2]
1.92(1)
1.93(1)
aj
[ReO(ECH3)]
RO -
1.69(1)
2.252(9)
101.2
980
al
[ReOCl(DEBT)2]
RO-
1.684(7)
2.138(5)
98.1
--
am
[ReOCl3 (dppmO)]
RO -
1.673(5)
2.127(4)
97.4
987
[ReOCl3 (OPPh3)(Me3Bzm)]
RO-
1.662(6)
2.081(7)
95.9
--
an
ao
This journal is © The Owner Societies 1999
Table S1a. Cont.
[{ReOCl2 (DPK.OH)}Cl]-
RO-
1.670(6)
[ReO(MAG2-oABAH)]-
-
1.684(4)
--
110.6
[ReO(MAG2-pABAH)]-
-
1.670(5)
--
111.0
[ReO(map)]- (syn)
-
1.662(5)
--
110.8
970
ar
ReOCl4-
-
1.64(4)
1.62(4)
--
105.2
104.9
1033
as
ReOCl4-
-
1.63(2)
100.0
1067
at
1.981(5)
--
95.8
953
ap
966
aq
970
aq
-------------------------------------------------------------------------------------------------------------------------------------cyclam= 1,4,8,11-tetraazacyclotetradecane; en= ethylenediamine; py= pyridine; PNH2= 2-(diphenylphoshinoκP)phenylazanide-κN; N(SPPH2)2= iminobis (diphenylphosphine sulphide); Haza= 7-azaindole; DEBT= N,Ndiethyl-N'-benzoylthiourea; dppd= dianionic form of N,N'-bis[2-(diphenylphosphino)phenyl]propane-1,3diamine; acac= anionic form of acetylacetone; B(pz)4= tetrakis(pyrazolyl)borate; L= {2'(NC4H3-2CH=N(CH2)3NMe(CH2)3CH=N-)C4H3NH}; PO= anionic form of o-hydroxyphenyl-diphenylphosphine; oz =
anionic form of 2-(2'-hydroxyphenyl)-2-oxazoline; salampH= -OC6H4-2-CH2-NH(CH2)3PPh2; salimp= -OC6H42-CH=N(CH2)3PPh2; L’= 2'-HOC6H4CH=NCH2CH2OCH2; Me-sal= N-methylsalicylideneiminate; Ph-sal= Nphenyl salicylideneiminate; salen= N,N'-ethylenebis(salicylideneiminate); L''= 1,3-(N,N'-bis-(3,5dichlorosalycilidene)diamino)-2,2-dimethylpropyl; L'''= 1,3-(N,N'-bis(salycilidene)diamino)-2,2dimethylpropyl; cat= catecholate; ma= maltolate; tu= thiourea; Acbhyz= acetone benzoylhydrazonide;
N(OPPH2)2= iminobis(diphenylphosphine oxide); ECH3= dianionic form of (2R,7R)-2,7-dicarboxy-3,6-diaza1,8-octanedithiol; dppmO= Ph2PCH2P(O)Ph2; Me3Bzm= 1,5,6-trimethylbenzilimidazole; DPK= di-(2pyridyl)ketone; MAG2-(o,p)ABAH= mercaptoacetylglycylglycyl-o,p-aminobenzoate; map= dianionic form of
2,3-bis(mercaptoacetamido)propanoate.
--------------------------------------------------------------------------------------------------------------------------------------
This journal is © The Owner Societies 1999
References of Table S1a
a) PIGBAI: Wang, Y-P.; Che, C-M.; Wong, K-Y.; Peng, J-M. Inorg. Chem. 1993, 32, 5827-5832;
b) PAJVUR: Luna, S.A.; Bolzati, C.; Duatti, A.; Zucchini, G.L.; Bandoli, G.; Refosco, F. Inorg.
Chem. 1992,31, 2595-2598;
c) OXPYRE10, REOENC02: Lock,C.J.L.; Turner, G. Acta Cryst. 1978, B34, 923-927;
d) GILFAI: Blake, A.J.; Greig, J.A.; Schröder, M. J. Chem. Soc. Dalton Trans. 1988, 2645-2647;
e) OEOPRE: Lock, C.J.L.; Turner, G. Can. J. Chem. 1977, 55, 333-339;
f) SUHGIL01: Bandoli, G.; Dolmella, A.; Tisato,F.; Refosco, F. Acta Cryst. 1994, C50, 530-532;
g) SUHGIL: Refosco, F.; Tisato, F.; Bandoli, G.; Bolzati, C.; Dolmella, A.; Moresco, A.;
Nicolini, M. J. Chem. Soc. Dalton Trans. 1993, 605-618;
h) ZEGHUO, ZEGJAW: Ciani, G.; D'Alfonso, G.; Romiti, P.; Sironi, A.; Freni, M. Inorg. Chim.
Acta 1983, 72, 29-37;
i) JIFWAW, JIFVOS: Rossi, R.; Marchi, A.; Magon, L.; Casellato, U.; Tamburini, S.; Graziani,
R. J. Chem. Soc. Dalton Trans. 1991, 263-268;
j) JOKYUD: Rossi, R.; Marchi, A.; Marvelli, L.; Peruzzini, M.; Casellato, U.; Graziani, R. J.
Chem. Soc. Dalton Trans. 1992, 435-437;
k) BEZFER01: Graziani, R.; Casellato, U.; Rossi, R.; Marchi, A. J. Cryst. Spectr. Res. 1985, 15,
573-579;
l) WERLEK: Lebuis, A.M.; Beauchamp, A.L. Acta Crystallogr., 1994, C50, 882-884;
m) YUHLUI: Abram, S.; Abram, U.; Schulz-Lang, E.; Strähle, J. Acta Crystallogr. 1995, C51,
1078-1080;
n) JUYBEK: Winkler Tsang, B.; Reibenspies, J.; Martell, A.E. Inorg. Chem. 1993, 32, 988-994;
o) JAXMAW: Purcell, W; Roodt, A.; Basson, S.S.; Leipoldt, J.G. Transition Met. Chem., 1989,
14, 5-6;
p) YOMNET, YOMNIX: Tisato, F.; Refosco, F.; Moresco, A.; Bandoli, G.; Dolmella, A.;
Bolzati,C. Inorg. Chem. 1995, 34, 1779-1783;
q) ZURNAB: Paulo, A.; Domingos, A.; Santos, I. Inorg. Chem. 1996, 35, 1798-1807;
r) JEZCIA: Banbery, H.J.; McQuillan, F.S.; Hamor, T.A.; Jones, C.J.; McCleverty, J.A.
Polyhedron, 1990, 9, 615-618;
s) YUBGOR: Luo,H.; Setyavati, I.; Rettig, S.J.; Orvig, C. Inorg. Chem. 1995, 34, 2287-2299;
t) NALNOD, NALPEV: Bolzati, C; Tisato, F.; Refosco, F.; Bandoli, G.; Dolmella, A. Inorg.
Chem. 1996, 35, 6221-6229;
u) ZOPYIM: Shuter, E.; Hoveyda, H.R.; Karunaratne, V.; Rettig, S.J.; Orvig, C. Inorg. Chem.
1996, 35, 368-372;
v) JITKAY, JITKEC: Banbery, H.J.; Hussain, W.; Hamor, T.A.; Jones, C.J.; McCleverty, J.A.
Polyhedron, 1991, 10, 243-247;
w) KAPWON: Banbery, H.J.; McQuillan, F.S.; Hamor, T.A.; Jones, C.J.; McCleverty, J.A. J.
Chem. Soc. Dalton Trans., 1989, 1405-1407;
x) BIMBUU10, CICXER: Bertolasi, V.; Ferretti,V.; Sacerdoti, M.; Marchi, A. Acta Cryst. 1984,
C40, 971-974;
y) BAXJIT: Gilli, G.; Sacerdoti, M.; Bertolasi, V.; Rossi,R. Acta Cryst. 1982, B38, 100-104;
z) BANFAX10: Bertolasi, V.; Sacerdoti, M.; Gilli, G.; Mazzi, U. Acta Cryst. 1982, B38, 426-429;
aa) Bombieri,G.; Mazzi, U.; Gilli, G.; Hernandez-Cano, F. J. Organom. Chem. 1978, 159, 53-62;
ab) BANFAX01: Sacerdoti, M.; Bertolasi, V.; Gilli, G.; Duatti, A. Acta Cryst. 1984, C40, 968970;
This journal is © The Owner Societies 1999
ac) ZURYUG, ZURZAN: Herrmann, W.A.; Rauch,M.U.; Artus, G.R.J. Inorg. Chem., 1996, 35,
1988-1991;
ad) HEFYEW: Kettler, P.B.; Chang, Y-D.; Zubieta,J.; Abrams, M.J. Inorg. Chim. Acta 1994,
218, 157-165;
ae) PIBDUZ, PIBDOT: Luo,H.; Rettig, S.J.; Orvig, C. Inorg. Chem. 1993, 32, 4491-4497;
af) XCACRE: Lock, C.J.L.; Wan, C. Can. J. Chem. 1975, 53, 1548-1553;
ag) OACTUR: Lis, T. Acta Cryst. 1976, B32, 2707-2709;
ah) FOAMDS10: Lis, T. Acta Crystallogr. 1979, B35, 3041-3044;
ai) VEPHIH: Purcell, W.; Roodt, A.; Basson, S.S.; Leipoldt, J.G. Transition Met. Chem., 1990, 15,
239-241;
aj) ABHPRE: Hursthouse, M.B.; Jayaweera, S.A.A.; Quick, A. J. Chem. Soc. Dalton Trans.
1979, 279-282;
ak) JUMLUY: Katti, V.K.; Barnes, C.L. Inorg. Chem. 1992, 31, 4231-4235;
al) YELTUE: Marzilli, L.G.; Banaszczyk, M.G.; Hansen, L.; Kuklenyik, Z.; Cini, R.; Taylor, A. Jr.
Inorg. Chem. 1994, 33, 4850-4860;
am) LALCUW: Dilworth, J.R.; Lewis, J.S.; Miller, J.R.; Zheng, Y. Polyhedron, 1993,12, 221-225;
an) YAYSUM: Shih, K-Y.; Fanwich, P.E.; Walton, R.A. Inorg. Chimica Acta, 1993, 212, 23-29;
ao) TAQFUM: Hansen, L.; Alessio, E.; Iwamoto, M.; Marzilli, P.; Marzilli, L.G. Inorg. Chimica
Acta, 1995, 240, 413-417;
ap) POGJGA: Bandoli, G.; Dolmella, A.; Gerber, T.I.A.; du Preez, J.G.H.; Kemp, H.J. Inorg.
Chimica Acta, 1994, 217, 141-147;
aq) VUKLOC, VUKLUI: Hansen, L.; Cini, R.; Taylor, A.Jr.; Marzilli, L.G. Inorg.Chem. 1992,
31, 2801-2808;
ar) SIDHIW: Rao, T.N.; Adhikesavalu, D.; Camerman, A.; Fritzberg, A.R. J. Am. Chem. Soc.
1990, 112, 5798-5804;
as) Edwards, A.J. J. Chem. Soc. Dalton Trans. 1972, 582;
at) ASPORC: Lis, T.; Jezowska-Trzebiatowska, B. Acta Cryst. 1977, B33, 1248-1250.
This journal is © The Owner Societies 1999
Table S1b. Selected bond distances (Å) and angles () and v(MO) IR stretching frequencies (cm-1) for Tc(V) oxo
and dioxo-complexes.
------------------------------------------------------------------------------------------------------------------------Compound
trans-ligand
d(MO)
d(M-O)
<α>
v(MO) Ref.
------------------------------------------------------------------------------------------------------------------------[TcO2(cyclam)]+
O2-
1.749(3)
1.754(3)
1.754(3)
1.754(3)
90.0
90.0
790
a
TcO2(pent)(AO)2
O2-
1.743(3)
1.746(3)
1.744(3)
1. 742(3)
90.1
90.6
790
b
1.748(6)
1.748(6)
90.0
1.737(6)
1.737(6)
90.0
821
c
[TcO2(TBP)4]+
O2-
[TcO2(en)2]+
O2-
1.741(1)
1.752(1)
90.7
833
d
TcOBr2(OEt)(Npy)2
EtO-
1.684(6)
1.855(6)
91.1
938
e
[TcO(OMe)(PPh2PhN)2]
MeO-
1.700(8)
1.999(8)
96.6
878
f
[TcO(OMe)(dppd)]
MeO-
1.691(2)
2.030(2)
98.3
882
g
TcO(aza-sal)
Ar-O-
1.685(6)
2.120(6)
99.4
888
h
TcO(apa)
Ar-O-
1.678(2)
2.149(2)
99.3
915
i
TcOCl(thoz)2
Ar-O-
TcOCl(Ph-sal)2
Ar-O-
1.67(1)
1.94(1)
95.1
940
[TcOCl3(hbt)]-
Ar-O-
1.650(6)
1.948(4)
94.2
945
TcO(OPh-sal)(quin)
Ar-O-
1.659(7)
2.014(6)
96.4
TcOCl(Me-quin)2
Ar-O-
[TcOCl3(ma)]-
Ar-O-
[TcO(ox)2(Hox)]2-
RCOO-
1.661(3)
1.649(3)
1.647(2)
1.978(3)
1.994(3)
2.019(2)
95.4
96.2
94.7
935
948
945
965
j
k
l
m
n
o
1.640(6)
2.069(6)
98.3
963
p
TcO(pam-N,S,O)(pam-N,S) RCOO-
1.657(4)
2.214(4)
100.8
958
q
[TcO(H2O)(acac)2(en)]+
H2 O
1.648(2)
2.282(2)
100.8
960
r
[TcO(H2O)(sacac)2(en)]+
H2 O
1.643(3)
2.384(2)
101.1
964
s
Ar-CHO
1.656(8)
2.359(8)
970
t
TcO(glusal)(sal)
102.4
[TcO(map)]- (syn)
-
1.656(7)
110.4
945
u
[TcO(map)]- (anti)
-
1.644(5)
110.8
950
u
[TcO(epa)]-
-
1.648(3)
104.1
965
v
This journal is © The Owner Societies 1999
Table S1b. Cont.
[TcO(PIC)]
-
1.653(4)
[TcOCl(L6)]
-
1.645(7)
108.8
980
x
[TcO(OPh-sal)]-
-
1.634(7)
111.6
980
y
1.610(4)
106.8
1016
z
TcOCl4-
-
109.2
965
w
--------------------------------------------------------------------------------------------------------------------------------------cyclam= 1,4,8,11-tetraazacyclotetradecane; pent(AO)2= 3,3,11,11-tetramethyl-4,10-diazatridecane-2,12-dione
dioximate; TBP= 4-tert-butylpyridine; en= ethylenediamine; Npy= 4-nitropyridine; dppd= dianionic form of
N,N'-bis[2-(diphenylphosphino)phenyl]propane-1,3-diamine; aza-sal= N,N’-3-azapentane-1,5-diylbis
(salicylideneiminate); apa= trianionic form of N,N'-azapentane-1,5-diylbis-(3-(1-iminoethyl)-6-methyl-2H-pyran2,4(3H)-dione; thoz= anionic form of 2-(2'-hydroxyphenyl)-2-thiazoline; Ph-sal= N-phenyl salicylideneiminate;
hbt= anionic form of 2-(2-hydroxypheyl)benzothiazole; OPh-sal= anionic form of 2-hydroxyphenylsalycylideneiminate; Me-quin= 2-methyl-8-quinolinolate; ma= maltolate; ox= oxalate; pam= penicillaminate;
(acac)2en= dianionic form of N,N’-ethylenebis(acetylacetone iminate); (sacac)2en = dianionic form of N,N’ethylenebis(acetylacetone thioimine); glusal= dianionic form of N-salicylidene-D-glucosamine; sal= anionic form of
salicylaldehyde; map= dianionic form of 2,3-bis (mercaptoacetamido)propanoate; H4epa= N,N'-ethylenebis(2phenoxyacetamide);
PIC= N-(2-((2-mercaptoacetyl)amino)ethyl)-2-pyridine carboxamide; H2L6= S-methyl-3-(2'-
hydroxy-1'-naphtylmethylene)-dithiocarbazate).
----------------------------------------------------------------------------------------------------------------------------------------
This journal is © The Owner Societies 1999
References of Table S1b
a) BAPPIR: Zuckman, S.A.; Freeman, G.M.; Troutner, D.E.; Volkert, W.A.; Holmes, R.A.; Van
Derveer, D.G.; Barefield, E.K. Inorg. Chem. 1981, 20, 2386-2389;
b) FONNOL: Jurisson, S.; Aston, K.; Fair, C.K.; Schlemper, E.O.; Sharp, P.R.; Troutner, D.E. Inorg.
Chem. 1987, 26, 3576-3582;
c) CURVOA: Kastner,M.E.; Fackler, P.H.; Clarke, M.J.; Deutsch, E. Inorg. Chem. 1984, 23, 4683-4688;
d) BEWRIE: Kastner, M.E.; Lindsay, M.J.; Clarke, M.J. Inorg. Chem. 1982, 21, 2037;
e) CUHXUY: Fackler, P.H.; Kastner, M.E.; Clarke, M.J. Inorg. Chem. 1984, 23, 3968-3972;
f) SUHGEH: Refosco, F.; Tisato, F.; Bandoli,G.; Bolzati, C.; Dolmella, A.; Moresco, A.; Nicolini, M.
J. Chem. Soc. Dalton Trans. 1993, 605-618;
g) YOMNAP: Tisato, F.; Refosco, F.; Moresco, A.; Bandoli, G.; Dolmella, A.; Bolzati, C. Inorg.
Chem. 1995, 34, 1779-1787;
h) FURWUK: Refosco, F.; Tisato, F.; Mazzi, U.; Bandoli, G.; Nicolini, M. J. Chem. Soc. Dalton
Trans. 1988, 611-615;
i) SOZVIM: Liu, S.; Rettig, S.J.; Orvig, C. Inorg. Chem. 1991, 30, 4915-4919;
j) ZOPYEI: Shuter, E.; Hoveyda, H.R.; Karunaratne, V.; Rettig,S.J.; Orvig, C. Inorg. Chem. 1996, 35,
368-372;
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This journal is © The Owner Societies 1999
Table S2. Effect of the diaminodithiolate and diaminooxymeoximate equatorial ligands on apical M-O multiple
bond (A), mean angle <α> (degrees) and IR v(MO) stretching frequency (cm-1).
Compound
d(MO)
<α>
v(MO)
Ref.
Re-complexes
ReO(Bn-MAMA’)
1.680(2)
110.5
980
a
syn-ReO(Bn-MAMA’)
1.683(4)
110.5
955
a
syn-ReO(BAT-PPP)
1.697(6)
1.701(6)
110.7
110.6
935
b
[ReO(EC-3N,4N)]3-
1.736(7)
109.2
872
c
meso-TcO[CB-PAO]
1.664(5)
110.1
931
a’
TcOPn(AO)2
1.679(3)
109.8
923
b’
TcOPn(AO)(AO-CH3)
1.671(3)
110.0
921
c’
TcOPn(AO-CH3)2
1.677(2)
109.7
920
c’
syn-TcO(BAT-PPP)
1.681(2)
110.9
919
d’
dl-TcO[(CH3)2Pn(AO-CH3)2]
1.682(5)
109.8
911
c’
meso-TcO[(CH3)2Pn(AO-CH3)2]
1.677(3)
1.670(4)
110.0
110.1
908
c’
anti-TcO(BAT-PPP)
1.691(8)
1.670(8)
111.1
110.7
900
d’
Tc-complexes
Bn-MAMA’= N-benzyl-monoaminemonoamide; BAT-PPP= bis(amino thio)-phenylpiperidine; EC= esaanionic form of
(2R, 7R)-2,7-dicarboxy-3,6-diaza-1,8-octanedithiol; CB-PAO= 4,8-diaza-3,9-dimethyl-6,6-trimethyleneundecane-2,10-dione
dioxime; Pn= propylene; AO = 3-amino-3-methyl-2-butanone oxime or amine oxime; Pn(AO)2 = 3,3,9,9-tetramethyl-4,8diazaundecane-2,10-dione oxime.
a) WEMKOO, WEMKUU: O’Neil, J.P.; Wilson, S.R.; Katzenellenbogen, J.A. Inorg. Chem. 1994, 33, 319-323; b)
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838-840; b’) CEWZIN10: Fair, C.K.; Troutner, D.E.; Schlemper, E.O.; Murmann, R.K.; Hoppe, M.L. Acta Crystallogr.,
1984, C40, 1544-1546; c’) DORMUS, DORNAZ, DORNED, DORNIH: Jurisson, S.; Schlemper, E.O.; Troutner, D.E.;
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This journal is © The Owner Societies 1999
Table S3. Proton affinities (PA), pKa values and pK1 values for trans-entering ligands. K1 = firstassociation equilibrium constant = [ML]/[M][L] where L= ligand and M= metal.
Ligand base
Coniugated acid
PAa
pKab
3+
Fe
pK1c
Th4+
TcO2+
1
O2-
OH-
—
_21
—
—
—
2
RCH2O-
RCH2OH
376.1
(EtOH)
16
—
—
—
3
OH-
H2 O
389.5
14.0*
4
MeO-
MeOH
379.2
15.2
5
ArO-
ArOH
351.4
8-11
6
acac-
acacH
_344
7
RCOO-
RCOOH
(AcCOOH)
348.5
8
F3CCOO-
F3CCOOH
322
9
H2O
10 ArCHO
H3O+
ArCHOH+
11.8
—
10.8
—
12.6
—
7.8(phenol) 8.4
8.9(cresol)
—
9
9.8
8.8
—
4.8
3.4
3.9
—
0.23
—
—
—
166.5
0.0*
—
0.2
—
199.3
-7
—
—
—
(*) Values of -1.74 for pKa (H3O+) and 15.74 for pKa (H2O) were adopted following the procedure
described in: Maskill, H. The Physical Bases of Organic Chemistry, Oxford Univ. Press: 1985, pp. 165
and 177.
Mallard, W.G.; Linstrom, P.J. Eds. ‘NIST Chemistry WebBook, NIST Standard Reference Database
Number 69', March 1998.
a
b
Ref. 12b.
Smith, R.M.; Martell, A.E. Eds. ‘Crytical Stability Constants’, Plenum Press: New York, 1975-1989;
Vols. 3,4,5,6.
c