Supplementary Material (ESI) for Dalton Transactions
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All reactions were performed under nitrogen with
exclusion of water and oxygen. [Cp°2ZrMe2]i and
[MCl2(PR3)2] (M = Ni, Pd)ii were prepared by literature
procedures. All reagents and solvents were purified by
standard procedures.
Synthesis of 1. A solution of mercaptoacetic acid
(0.23 ml, 3.28 mmol) in toluene (15 mL) was added to a
solution of [Cp°2ZrMe2] (0.69 g, 1.64 mmol) in toluene (15
mL). The colorless solution was stirred for 3 h, then the
solvent was reduced in vacuum to about half its volume.
Cooling to –20°C yielded 1 as colorless, moderately airsensitive crystals (0.86 g, 92%), mp 159-162 °C (Found:
C, 54.2; H, 7.4%. ZrS2O4C26H40 requires C, 54.6; H, 7.1%);
H(CD2Cl2, 400 MHz, 25°C) 0.86 [6H, t, 3J(HH) 7.5 Hz,
C5Me4CH2CH3], 1.83 [12 H, s, C5Et(CH3)4], 1.85 [12 H, s,
C5Et(CH3)4], 2.07 [2 H, t,
3
J(HH) 6.7 Hz, SH], 2.30 [4 H,
q, 3J(HH) 7.5 Hz, C5Me4CH2CH3], 3.29 [4 H, d,
3
J(HH) 6.7
Hz, CH2SH]; C(CD2Cl2, 100.6 MHz, 25°C) 10.7 and 11.0 [s,
C5Et(CH3)4], 14.2 (s, C5Me4CH2CH3), 19.2 (s, C5Me4CH2CH3),
29.7 (s, OOCCH2SH), 121.4, 122.4, 127.4 (s, C5EtMe4),
178.0 (s, OOCCH2SH); IR (KBr): (tilde)= 1641 (C=O), 1539,
1339 (O-C-O), 1223 cm-1 (C-O); EI-MS: m/z 480
[Cp°2ZrOOCCH2SH]+, 421 [Cp°2ZrOO]+, 405 [Cp°2ZrO]+, 389
[Cp°2Zr]+, 91 [OOCCH2SH]+, 47 [CH2SH]+.
Supplementary Material (ESI) for Dalton Transactions
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Synthesis of 2. A solution of [NiCl2(PMe2Ph)2] (0.23
g, 0.57 mmol) in toluene (15 mL) was added to a solution
of 1 (0.32 g, 0.56 mmol) and NEt3 (0.16 mL, 1.12 mmol) in
toluene (15 mL). The color changed from colorless to
green-brown. After stirring for 12 h, NEt3HCl was filtered
off and the mother liquor was concentrated to 15 mL.
Addition of petroleum ether (40 mL) gave 2 as a green
solid. Recrystallization from THF at –20 °C gave green
crystals of 2 (0.30 g, 64%), mp > 300 °C (Found: C, 53.4;
H, 7.0; S, 7.4%. Zr2Ni2S4P2O8C68H982THF requires C, 54.4; H,
6.9; S, 7.6%); H(C6D6, 400 MHz, 25°C) 0.87 [12 H, t,
3J(HH)
7.5 Hz, C5Me4CH2CH3], 1.45 [12 H, d, 2J(HP) 9.8 Hz,
PCH3], 1.76 [12 H, s, C5Et(CH3)4], 1.78 [12 H, s,
C5Et(CH3)4], 1.83 [12 H, s, C5Et(CH3)4], 1.85 [12 H, s,
C5Et(CH3)4], 2.35 [8 H, m,
3J(HH)
7.5 Hz, C5Me4CH2CH3], 3.68
[4 H, s, OOCCH2S), 3.85 (4 H, s, OOCCH2S), 7.99 (4 H, br
t, PC6H5), signals of phenyl groups partly obscured by
solvent; C(C6D6, 100.6 MHz, 25°C) 11.6, 11.7, 11.9 [s,
C5Et(CH3)4], 13.8 [d,
1J(CP)
34.3 Hz, PCH3], 15.2 (s,
C5Me4CH2CH3), 20.0 (s, C5Me4CH2CH3), 33.2, 38.6 (s,
OOCCH2S), 121.1, 122.0, 122.7, 123.0, 127.8 (s, C5EtMe4),
130.0, 132.1 (s, PC6H5), 189.9, 192.7 (s, OOCCH2S);
P(C6D6, 162 MHz, 25°C) 1.3 (s, PMe2Ph); IR (KBr):
(tilde)= 1549 (O-C-O) cm-1, overlap of s(O-C-O) with
s(C=C) and (CH) in the range 1455-1405 cm-1.
Supplementary Material (ESI) for Dalton Transactions
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Synthesis of 2b. A solution of [NiCl2(PnBu3)2] (0.78
g, 1.47 mmol) in toluene (15 mL) was added to a solution
of 1 (0.84 g, 1.47 mmol) and NEt3 (0.41 mL, 2.9 mmol) in
toluene (15 mL). The color changed from colorless to
green-brown. After stirring for 12 h, NEt3HCl was filtered
off and the mother liquor was concentrated to 1 mL.
Addition of pentane (40 mL) gave 2b as a green solid
(0.90 g, 74%), mp 135-140 °C (Found: C, 53.8; H, 8.7; S,
7.1%. Zr2Ni2S4P2O8C76H130 requires C, 55.0; H, 7.8; S, 7.7%);
H(C6D6, 400 MHz, 25°C) 0.90 [12 H, t, 3J(HH) 7.4 Hz,
C5Me4CH2CH3], 0.97 [18 H, t, 3J(HH) 7.3 Hz, PCH2CH2CH2CH3],
1.50 [12 H, sext,
3J(HH)
7.2 Hz, PCH2CH2CH2CH3], 1.77 [12
H, br. m, PCH2CH2CH2CH3], 1.88-1.85 [12 H, br. m,
PCH2CH2CH2CH3], 1.81 [12 H, s, C5Et(CH3)4], 1.82 [12 H, s,
C5Et(CH3)4], 1.87 [12 H, s, C5Et(CH3)4], 1.90 [12 H, s,
C5Et(CH3)4], 2.35 [8 H, m,
3J(HH)
7.3 Hz, C5Me4CH2CH3], 3.70
[4 H, s, OOCCH2S), 3.86 (4 H, s, OOCCH2S); C(C6D6, 100.6
MHz, 25°C) 11.6, 11.7, 11.91, 11.93 [s, C5Et(CH3)4], 14.7
[s, PCH2CH2CH2CH3], 15.2 (s, C5Me4CH2CH3), 20.0 (s,
C5Me4CH2CH3), 24.0 [d,
1J(CP)
28.1 Hz, PCH2CH2CH2CH3], 25.7
[d, 3J(CP) 12.8 Hz, PCH2CH2CH2CH3], 27.5 [s, PCH2CH2CH2CH3],
32.7 [d, 3J(CP) 4.4 Hz, OOCCH2S], 38.3 [d,
3J(CP)
6.6 Hz,
OOCCH2S], 121.2, 121.9, 122.7, 122.9, 127.8 (s, C5EtMe4),
190.0, 192.6 (s, OOCCH2S); P(C6D6, 162 MHz, 25°C) 12.8 (s,
PnBu3); IR (KBr): (tilde)= 1538 (O-C-O) cm-1, overlap of
Supplementary Material (ESI) for Dalton Transactions
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s(O-C-O) with s(C=C) and (CH) in the range 1455-1407
cm-1.
Synthesis of 3. A solution of [PdCl2(PnBu3)2] (0.33
g, 0.58 mmol) in toluene (10 mL) was added to a solution
of 1 (0.33 g, 0.58 mmol) and NEt3 (0.16 ml, 1.12 mmol) in
toluene (15 mL). The color changed from colorless to
bright orange. After stirring for 12 h, NEt3HCl was
filtered off and petroleum ether (10 mL) was added to the
mother liquor. Cooling to 4 °C gave orange needles of 3.
Recrystallization from THF/pentane at 4 °C gave a small
amount of orange crystals of 3 suitable for crystal
structure determination; mp 240 °C (decomp); there are
numerous signals and extensive overlap of signals in the
1H
and
13C
NMR spectra. Therefore, only signal ranges are
given. H(C6D6, 400 MHz, 25°C) 0.8-1.9 (PCH2CH2CH2CH3 and
C5Me4CH2CH3), 2.0-2.2 [C5Et(CH3)4], 2.2-2.6 (C5Me4CH2CH3),
3.7-3.8 (OOCCH2S); C(C6D6, 100.6 MHz, 25°C) 11.7-12.1
[C5Et(CH3)4], 14.6, 14.8, 15.2 (s, PCH2CH2CH2CH3 and
C5Me4CH2CH3), 20.1, 20.2 (s, C5Me4CH2CH3), 24.6-27.8
(PCH2CH2CH2CH3), 121-128 (C5EtMe4), 175.0, 188.3, 190.0,
191.1 (s, OOCCH2S); P(C6D6, 162 MHz, 25°C) 18.5 [d,
4J(PP)
5.3 Hz, PnBu3], 17.8 [d, 4J(PP) 5.3 Hz, PnBu3]; IR (KBr):
(tilde) = 1651 (C=O), 1519, 1296 (O-C-O), 1196 cm-1 (CO).
Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2002
i R. S. Threlkel, J. E. Bercaw, J. Organomet. Chem. 1977,
136, 1.
ii H. Köpf, Chem. Ber. 1981, 114, 2731.