J.C. Thomas, J.C. Peters / Polyhedron 23 (2004) 489–497
491
resulting solution, providing white solid 2 (193.2 mg,
73.5%). Clear, colorless block crystals suitable for X-ray
diffraction were obtained from pentane diffusion into a
1h, the sulfur had been visibly consumed and the reac-
tion changed color from colorless to yellow. The reac-
tion mixture was filtered, and volatiles were removed
under reduced pressure, providing pale yellow solid 4
(160.7 mg, 97.2%) in > 95% purity. Analytically pure 4
has not yet been isolated. 1H NMR (300 MHz, acetone-
d6): d 7.62 (br, 4H), 7.46 (br, 4H), 6.8–7.3 (m, 24H), 6.62
(m, 3H), 3.36 (m, 8H, [(CH3CH2CH2CH2)4N]), 1.76 (m,
8H, [(CH3CH2CH2CH2)4N]), 1.6 (br, 4H, [[PhB(CH2P
(S)Ph2)(CH2PPh2)2]PtMe2]), 1.39 (m, 8H, [(CH3CH2
CH2CH2)4N]), 0.96 (t, 12H, [(CH3CH2CH2CH2)4N]),
0.73 (br, 2H, [[PhB(CH2P(S)Ph2)(CH2PPh2)2]PtMe2]),
1
THF solution of 2. H NMR (300 MHz, C6D6): d 7.90
(d, 2H, [ortho-C6H5BP3]), 7.54 (t, 2H, [meta-C6H5BP3]),
7.36 (m, 13H, aryl protons), 6.85 (m, 18H, aryl protons),
2.01 (br, 6H, [PhB(CH2PPh2)3]), 1.35 (d, 9H, Pt(CH3)3,
3
2JPt–H ¼ 55:5 Hz, JP–H ¼ 7:2 Hz). 13C{1H} NMR
(125.7 MHz, C6D6): d 136.9, 133.9, 132.4, 129.5, 128.9,
124.9, 15.8 (br, [PhB(CH2PPh2)3]), 6.5 (dd, Pt(CH3)3,
2
1JPt–C ¼ 497 Hz, JP–C ¼ 11, 111 Hz). 31P{1H} NMR
(121.4 MHz, C6D6): d )26.01 (1JPt–P ¼ 1094 Hz).
11B{1H} NMR (128.3 MHz, C6D6): d )11.9. Anal. Calc.
for C48H50BP3Pt: C, 62.28; H, 5.44. Found: C, 62.44; H,
5.67%.
2
3
0.07 (t, 6H, Pt(CH3)2, JPt–H ¼ 68 Hz, JP–H ¼ 5 Hz).
31P{1H} NMR (121.4 MHz, acetone-d6): d 44.44 (s, 1P),
1
18.37 (s, 2P, JPt–P ¼ 1875 Hz).
2.2.3. [[j2-PhBP3]PtMe2][TBA] (3)
Solid off-white [PhBP3][TBA] (1.6076 g, 1.732 mmol)
2.2.5. [[j2-PhB(CH2P(BH3)Ph2)(CH2PPh2)2]PtMe2]
[TBA] (5)
was dissolved in THF (8 mL).
A
solution of
Solid 3 (241.2 mg, 0.2092 mmol) was added to a fresh
2 M solution of BH3 ꢁ SMe2 (104.6 lL, 0.2092 mmol) in
toluene/THF. After 5 min, concentration of the reaction
mixture under reduced pressure followed by addition of
petroleum ether precipitated solid 5. Analytically pure 5
was obtained from repeated washing of the solids with
petroleum ether (237.6 mg, 97.3%). 1H NMR (500 MHz,
CD2Cl2): d 7.72, 7.49, 7.0–7.4, 6.95, 6.54 (m, 35H, aryl
protons), 2.96 (m, 8H, [(CH3CH2CH2CH2)4N]), 1.50
(m, 8H, [(CH3CH2CH2CH2)4N]), 1.35 (m, 8H, [(CH3
CH2CH2CH2)4N]), 0.99 (t, 12H, [(CH3CH2CH2
(COD)PtMe2 (577.0 mg, 1.731 mmol) dissolved in THF
(1 mL) was added to the stirring [PhBP3][TBA] solution,
forming a colorless to pale yellow solution. After stirring
the reaction mixture for 4 h, the volume of the reaction
was reduced by removal of volatiles under reduced
pressure. Precipitation with pentane produced off-white
to pale yellow solids which were repeatedly triturated
with pentane. Drying the solids under reduced pressure
resulted in off-white to pale yellow solid 3 (1.8024 g,
90.3%). Clear, colorless rectangular prism crystals suit-
able for X-ray diffraction were grown by slow evapo-
2
CH2)4N]), 0.04 (t, 6H, Pt(CH3)2, JPt–H ¼ 67 Hz,
1
ration of a saturated toluene solution of 3. H NMR
3JP–H ¼ 5:5 Hz). 13C{1H} NMR (125.7 MHz, CD2Cl2):
d 161 (br), 140.1 (m), 137.5 (d), 137.2 (d), 134.7 (m),
133.9 (m), 133.3, 132.4 (d), 129.0, 128.4, 128.0, 127.8 (d),
127.5, 127.1, 125.5, 122.3, 59.3 ([(CH3CH2CH2
CH2)4N]), 24.3 ([(CH3CH2CH2CH2)4N]), 23.5 (br), 22.5
(br), 20.2 ([(CH3CH2CH2CH2)4N]), 13.9 ([(CH3CH2
(300 MHz, acetone-d6): d 7.64 (br, 4H), 7.44 (br, 4H),
6.86–7.28 (m, 24H), 6.63 (m, 3H), 3.36 (m, 8H,
[(CH3CH2CH2CH2)4N]), 1.76 (m, 8H, [(CH3CH2
CH2CH2)4N]), 1.55 (br, 4H, [[PhB(CH2PPh2)(CH2
PPh2)2]PtMe2]), 1.39 (m, 8H, [(CH3CH2CH2CH2)4N]),
0.96 (t, 12H, [(CH3CH2CH2CH2)4N]), 0.65 (br, 2H,
[[PhB(CH2PPh2)(CH2PPh2)2]PtMe2]), 0.08 (t, 6H,
1
CH2CH2)4N]), 5.1 (dd, Pt(CH3)2, JPt–C ¼ 602 Hz,
2JP–C ¼ 9:1, 102 Hz). 31P{1H} NMR (121.4 MHz,
2
3
1
Pt(CH3)2, JPt–H ¼ 67 Hz, JP–H ¼ 5 Hz). 13C{1H }
NMR (125.7 MHz, acetone-d6): d 122–148 (aryl car-
bons), 59.9 ([(CH3CH2CH2CH2)4N]), 25.0 ([(CH3CH2
CD2Cl2): d 18.01 (s, 2P, JPt–P ¼ 1878 Hz), 15.30 (br,
1P). 11B{1H} NMR (160.4 MHz, CD2Cl2): d )14.8,
)30.3. Anal. Calc. for C63H86B2NP3Pt: C, 65.09; H,
7.51; N, 1.19. Found: C, 64.69; H, 7.53; N, 1.02%.
CH2CH2)4N]), 24 (br), 21.0 ([(CH3CH2CH2CH2)4N]),
1
14.6 ([(CH3CH2CH2CH2)4N]), 6.7 (Pt(CH3)2, JPt–C
¼
2
616 Hz, JP–C ¼ 8:8, 103 Hz). 31P{1H} NMR (121.4
2.2.6. [[j2-PhB(CH2P(BH3)Ph2)(CH2PPh2)2]Pt(l-H)]2
[TBA]2 (6)
1
MHz, acetone-d6): d 18.96 (s, 2P, JPt–P ¼ 1888 Hz),
)9.61 (s, 0.12P), )12.60 (s, 0.88P). 11B{1H} NMR (160.4
Solid 3 (277.4 mg, 0.2377 mmol) was dissolved in
THF (2 mL). While stirring the reaction mixture, a fresh
2 M solution of BH3 ꢁ SMe2 in toluene/THF was added
(250 lL, 0.500 mmol). After 15 min, the solution was
concentrated to dryness under reduced pressure. The
resulting solids were washed with petroleum ether [5 ꢂ 2
mL] and dried under reduced pressure, providing ana-
lytically pure 6 (268.4 mg, 99.2%). 1H NMR (500 MHz,
C6D6): d 7.97 (br), 7.83 (m), 7.76 (br), 7.54 (br), 7.45 (d),
7.04 (br), 6.93 (m), (m, 35H, aryl protons), 2.66 (m, 8H,
[(CH3CH2CH2CH2)4N]), 2.10 (br, 4H), 1.61 (br, 2H),
MHz, acetone-d6):
C63H83BNP3Pt: C, 65.86; H, 7.34; N, 1.20. Found: C,
d
)14.10. Anal. Calc. for
65.51; H, 7.29; N, 1.06%.
2.2.4.
[TBA] (4)
[[j2-PhB(CH2P(S)Ph2)(CH2PPh2)2]PtMe2]
Solid 3 (159.0 mg, 0.1379 mmol) was dissolved in
THF (2 mL). While stirring the reaction mixture, a
suspension of elemental sulfur (4.6 mg, 0.14 mmol of S
atoms) in THF (1 mL) was added to the reaction. After