Silanethiolato Complexes
Mn(SSiPh3)2(tmeda) (4). The same procedure as used for 3d
was followed. Reaction of Mn[N(SiMe3)2]2 (0.29 g, 0.77 mmol)
and triphenylsilanethiol (0.43 g, 1.5 mmol) in the presence of
TMEDA (0.22 mL, 1.5 mmol) in Et2O (25 mL) yielded 0.42 g of
4 as colorless crystals in 72%. Anal. Calcd for C42H46MnN2S2Si2:
C, 66.90; H, 6.15; N, 3.71; S, 8.50. Found: C, 66.84; H, 6.15; N,
[FeCl4] (0.24 g, 0.52 mmol) in CH3CN (25 mL). The resulting
homogeneous solution was stirred for 20 min at room temperature.
The resulting brown solution was concentrated in vacuo, and then
addition of Et2O (30 mL) to the solution caused the separation of
a colorless powder. This material was isolated by decantation and
dried in vacuo to give 8 in 91% yield (0.51 g). Anal. Calcd for
C52H70Cl4Fe2N2S2Si2: C, 56.94; H, 6.43; N, 2.55; S, 5.85. Found:
1
3.73; S, 8.33. H NMR (CDCl3): δ 7.6 (∆ν1/2 ) 240 Hz, br). IR
1
(Nujol): 3065 (m), 3048 (m), 1584 (w), 1567 (w), 1429 (s), 1355
(w), 1287 (m), 1262 (w), 1193 (w), 1185 (w), 1167 (w), 1156 (w),
1125 (w), 1105 (s), 1063 (w), 1024 (m), 1007 (w), 997 (w), 950
(m), 793 (m), 743 (s), 736 (m), 702 (s), 683 (s), 622 (w), 565 (s),
C, 56.76; H, 6.35; N, 2.72; S, 5.77. H NMR (CD3CN): δ 8.27
(∆ν1/2 ) 24 Hz, br), 6.69 (∆ν1/2 ) 31 Hz, br), 6.54 (∆ν1/2 ) 220
Hz, br), 2.97 (∆ν1/2 ) 25 Hz, br, CH3CH2N), 1.20 (∆ν1/2 ) 20 Hz,
br, CH3CH2N). IR (Nujol): 1579 (m), 1435 (s), 1306 (w), 1265
(w), 1099 (s), 1031 (w), 998 (w), 875 (w), 844 (w), 821 (w), 743
(m), 733 (s), 705 (s), 690 (s), 611 (m), 534 (s), 521 (m), 481 (m)
cm-1. UV-visible (λmax, nm (ꢀ, M-1 cm-1), CH3CN): 294 sh
(5400), 250 sh.
503 (s), 489 (s), 436 (m), 428 (w) cm-1
.
Co(SSiPh3)2(tmeda) (5). Addition of a Et2O (20 mL) solution
of triphenylsilanethiol (0.43 g, 1.5 mmol) into a mixture of Co-
[N(SiMe3)2]2 (0.28 g, 0.74 mmol) and TMEDA (0.22 mL, 1.5
mmol) in Et2O (10 mL) followed by workup similar to 3d afforded
0.39 g of 5 as blue crystals (70%). Anal. Calcd for C42H46CoN2S2-
Si2: C, 66.54; H, 6.12; N, 3.70; S, 8.46. Found: C, 66.25; H, 6.05;
[Ph3SiSLi(thf)]4. A solution of Ph3SiCl (10.0 g, 33.9 mmol) in
THF (80 mL) was added to an excess of Li (2.30 g, 0.33 mol) in
THF (40 mL) at -78 °C. The reaction mixture was allowed to
warm slowly to room temperature and was stirred for 12 h. The
mixture was added to a suspension of sulfur (1.08 g, 33.7 mmol)
in THF (20 mL) at -78 °C. The reaction mixture was stirred at
room temperature for an additional 12 h. The yellow solution was
evaporated to dryness. The residue was extracted with toluene (120
mL) and centrifuged to remove LiCl. The supernatant was
concentrated under vacuum to afford yellow crystals of [Ph3SiSLi-
(thf)]4 (8.21 g, 65%). According to the X-ray study, the lithium
salt has a cubane geometry, where vertexes are occupied by sulfur
atoms and lithium atoms in an alternative manner. Crystal data:
tetragonal, space group P421c (No. 144), a ) b ) 15.665(8) Å, c
) 17.182(9) Å, V ) 4216(3) Å3, Z ) 8, Dc ) 0.990 Mg/m-3, Mo
KR, µ ) 2.07 cm-1, R(Rw) ) 0.085(0.087), GOF ) 1.17. Anal.
Calcd for C88H92O4Li4Si4S4: C, 71.32; H, 6.26; S, 8.65. Found:
1
N, 3.62; S, 8.05. H NMR (CDCl3): δ 7.25 (∆ν1/2 ) 20 Hz, br),
5.38 (∆ν1/2 ) 85 Hz, br), 5.22 (∆ν1/2 ) 16 Hz, br). IR (Nujol):
3062 (m), 1585 (w), 1566 (w), 1428 (s), 1305 (w), 1286 (m), 1262
(w), 1187 (w), 1102 (s), 1043 (w), 1025 (m), 998 (w), 950 (m),
798 (m), 747 (m), 739 (m), 699 (s), 684 (m), 622 (w), 563 (s), 507
(s), 495 (s), 467 (w), 431 (m), 418 (m) cm-1. UV-visible (λmax
,
nm (ꢀ, M-1 cm-1), CH2Cl2): 684 (750), 572 (180), 362 (3300),
312 (4700), 260 sh.
Ni(SSiPh3)2(tmeda) (6). To a suspension of [Ni(NPh2)]2 (0.39
g, 0.49 mmol) in toluene (15 mL) containing TMEDA (0.30 mL,
2.0 mmol) was added triphenylsilanethiol (0.59 g, 2.0 mmol) in
toluene (15 mL). The mixture immediately became a dark yellow
homogeneous solution that was stirred for 10 min at room
temperature. After the solution was centrifuged to remove a small
amount of an insoluble solid, the supernatant was evaporated to
dryness. The resulting residue was washed with Et2O/hexane (1:1)
to give 0.31 g of 6 as a yellow powder in 41% yield. Anal. Calcd
for C42H46N2NiS2Si2: C, 66.57; H, 6.12; N, 3.70; S, 8.46. Found:
1
C, 70.91; H, 6.45; S, 9.07. H NMR (C6D6): δ 8.1 (m, 36H, Ph),
7.2 (m, 24H, Ph), 1.86 (br, 16H, thf), 3.75 (br, 16H, thf). IR
(Nujol): 3063 (m), 3045 (m), 1427 (s), 1260 (w), 1183 (w), 1104
(s), 1045 (m), 896 (w), 743 (m), 701 (s), 686 (m), 622 (w), 575
(s), 499 (s), 431 (w) cm-1
.
1
C, 65.92; H, 5.91; N, 3.69; S, 8.38. H NMR (CDCl3): δ 10.35
(∆ν1/2 ) 98 Hz, br), 8.74 (∆ν1/2 ) 20 Hz, br), 7.16 (∆ν1/2 ) 16
Hz, br). IR (Nujol): 3064 (m), 1428 (s), 1106 (s), 1018 (w), 951
(w), 802 (w), 743 (m), 704 (s), 683 (m), 621 (w), 569 (s), 560 (s),
502 (s), 490 (s), 436 (w) cm-1. UV-visible (λmax, nm (ꢀ, M-1
cm-1), CH2Cl2): 543 (200), 433 (4900), 402 sh (2900), 378 sh
(2100), 345 sh (1200), 264 sh.
Cu4(SSiPh3)4 (9). Method 1. A solution of [Cu(CH3CN)4](PF6)
(0.27 g, 0.72 mmol) in CH3CN (15 mL) was added to a slurry of
3a (0.26 g, 0.36 mmol) in CH3CN (10 mL). The solution was stirred
at room temperature for 15 min, during which time a colorless
crystalline solid precipitated. The resulting solid was isolated by
decantation. Recrystallization from toluene yielded 9 as colorless
crystals (0.21 g, 81%).
(PPh4)2[MoS4{Fe(SSiPh3)2}2] (7). Addition of (PPh4)2[MoS4]
(0.28 g, 0.31 mmol) in CH3CN (25 mL) to a slurry of 3a (0.45 g,
0.62 mmol) in CH3CN (10 mL) immediately gave a homogeneous
dark red solution. The mixture was stirred for 20 h at room
temperature and evaporated to dryness. The residue was washed
with Et2O (15 mL) and then dissolved in CH2Cl2 (15 mL). The
solution was centrifuged to remove an insoluble material. The
supernatant was concentrated, and Et2O was added. Cooling the
solution to -25 °C gave black microcrystals of 7‚CH2Cl2 (0.50 g,
71%). Anal. Calcd for C121H102Cl2Fe2MoP2S8Si4: C, 64.15; H, 4.54;
S, 11.32. Found: C, 64.48; H, 4.70; S, 10.91. 1H NMR (CD3CN):
δ 11.44 (∆ν1/2 ) 370 Hz, br), 8.94 (∆ν1/2 ) 71 Hz, br), 7.86 (∆ν1/2
) 23 Hz, br), 7.65 (∆ν1/2 ) 53 Hz, br), 6.68 (∆ν1/2 ) 38 Hz, br),
5.45 (s, CH2Cl2). IR (Nujol): 1584 (w), 1426 (s), 1183 (w), 1105
(s), 1027 (w), 996 (w), 741 (m), 723 (s), 699 (s), 689 (s), 681 (s),
621 (w), 553 (s), 526 (s), 501 (s), 468 (w), 459 (w), 423 (w), 413
(w, Mo-S) cm-1. UV-visible (λmax, nm (ꢀ, M-1 cm-1), CH2Cl2):
611 sh (1300), 499 (12000), 387 sh (13000), 349 sh (16000), 319
(19000), 262 sh.
Method 2. Addition of a CH3CN (25 mL) solution of [Cu(CH3-
CN)4](PF6) (1.18 g, 3.17 mmol) into [Ph3SiSLi(thf)]4 (1.19 g, 0.80
mmol) in toluene (25 mL) followed by a workup analogous to
method 1 produced 0.83 g of 9 in 73% yield. Anal. Calcd for
C72H60Cu4S4Si4: C, 60.90; H, 4.26; S, 9.03. Found: C, 60.82; H,
4.21; S, 8.76. 1H NMR (500 MHz, CDCl3): δ 7.44 (m, 24H, Ph),
7.36 (m, 11H, Ph), 7.21 (m, 19H, Ph). IR (Nujol): 1586 (w), 1426
(s), 1302 (w), 1260 (w), 1186 (w), 1109 (s), 1029 (w), 997 (w),
850 (w), 738 (m), 708 (s), 696 (s), 681 (m), 620 (w), 542 (s), 533
(s), 501 (s), 490 (s), 429 (m) cm-1. UV-visible (λmax, nm (ꢀ, M-1
cm-1), CH2Cl2): 284 sh (19000), 270 sh (21000).
Reaction of Co(SSiPh3)2(tmeda) with (NBu4)F. To a mixture
of 5 (0.29 g, 0.38 mmol) in THF (20 mL) and PPh3 (0.20 g, 0.76
mmol) in THF (10 mL) was added slowly (NBu4)F (0.75 mL, 1.0
M THF solution). The deep blue solution immediately turned black.
After being stirred for 2 h, the solution was evaporated to dryness.
The remaining oil was extracted with CH3CN and the solvent was
removed. To the residue was added toluene and the mixture was
centrifuged to remove insoluble materials. After evaporation, the
resulting solid was extracted with CH2Cl2 (7 mL) and Et2O was
(NEt4)2[Fe2(SSiPh3)2Cl4] (8). To a suspension of 3a (0.37 g,
0.51 mmol) in CH3CN (10 mL) was added a solution of (NEt4)2-
Inorganic Chemistry, Vol. 41, No. 20, 2002 5085