1σ4,2σx-Diphosphetes (x ) 2-6)
J. Am. Chem. Soc., Vol. 119, No. 41, 1997 9727
(d, JPC ) 3.5 Hz, CH3CHN), 25.19 (d, JPC ) 2.8 Hz, CH3CHN), 31.50
(dd, JPC ) 4.0 and 1.7 Hz, CH3C), 41.84 (dd, JPC ) 13.7 and 47.8 Hz,
CH3C), 49.79 (d, JPC ) 3.0 Hz, CH3CHN), 135.46 (dd, JPC ) 18.3 and
25.6 Hz, PCSi), 194.89 (dd, JPC ) 22.6 and 53.3 Hz, PCt-Bu); 31P
NMR (CDCl3, 81.015 MHz) δ +59.19 (dq, JPP ) 47.1 Hz, JPH ) 10.0
Hz, σ4-P), +83.22 (d, JPP ) 47.1 Hz, JPSe ) 698.9 Hz, PSe2); 77Se
NMR (CDCl3, 76.323 MHz) δ +264.78 (d, JPSe ) 698.9 Hz); CIMS
m/e 577 (M+ + 1). Anal. Calcd for C21H46N2P2Se2S: C, 43.90; H,
8.07; N, 4.88. Found: C, 43.69; H, 7.82; N, 4.68.
Calcd for C29H49N2Cl4F3O5P2SSi: C, 42.13; H, 5.97; N, 3.39. Found:
C, 42.40; H, 6.14; N, 3.20.
1σ4,2σ6-Diphosphete 10. An ether solution (1 mL) of TCBQ (0.34
g, 1.40 mmol) was added dropwise, at -78 °C, to an ether solution (2
mL) of 1 (0.29 g, 0.70 mmol). The solution was allowed to warm to
room temperature, the solvent was removed under vacuum, and the
residue was extracted with pentane (3 × 5 mL). 10 was isolated by
crystallization from a CH2Cl2 solution at -30 °C as colorless crystals
(0.59 g, 92% yield): mp 223-224 °C; 1H NMR (CDCl3, 200 MHz) δ
0.46 (s, 9 H, CH3Si), 1.16 (d, JHH ) 8.5 Hz, 6 H, CH3CHN), 1.20 (d,
JHH ) 8.6 Hz, 6 H, CH3CHN), 1.26 (s, 9 H, CH3C), 1.50 (d, JHH ) 6.3
Hz, 6 H, CH3CHN), 1.53 (d, JHH ) 6.4 Hz, 6 H, CH3CHN), 3.84 (sept
d, JPH ) 9.0 Hz, JHH ) 6.9 Hz, 2 H, CH3CHN), 4.24 (sept d, JPH ) 9.0
Hz, JHH ) 6.9 Hz, 2 H, CH3CHN); 13C NMR (CDCl3, 50.323 MHz) δ
5.09 (dd, JPC ) 1.7 and 2.1 Hz, CH3Si), 23.84 (dd, JPC ) 3.4 and 1.9
Hz, CH3CHN), 25.24 (dd, JPC ) 3.6 and 1.3 Hz, CH3CHN), 25.37
(dd, JPC ) 3.4 and 2.1 Hz, CH3CHN), 25.60 (dd, JPC ) 2.1 and 1.3
Hz, CH3CHN), 31.29 (dd, JPC ) 3.8 and 1.4 Hz, CH3C), 40.10 (dd,
JPC ) 15.4 and 55.1 Hz, CH3C), 49.31 (dd, JPC ) 4.5 and 1.8 Hz,
CH3CHN), 50.86 (d, JPC ) 4.3 Hz, CH3CHN), 113.32 (d, JPC ) 8.6
Hz, OCC), 113.64 (dd, JPC ) 13.5 and 5.3 Hz, OCC), 114.25 (d, JPC
) 14.1 Hz, OCC), 114.49 (dd, JPC ) 9.1 and 1.9 Hz, OCC), 121.73,
122.25, 122.52, 122.57 (s, OCCC), 130.50 (dd, JPC ) 13.9 and 39.2
1σ4,2σ4-Diphosphete 7. A CH2Cl2 solution (1 mL) of bis(trimeth-
ylsilyl)peroxide (0.41 g, 2.28 mmol) was added dropwise, at -78 °C,
to a CH2Cl2 solution (1 mL) of 1 (0.32 g, 0.76 mmol). The solution
was allowed to warm to room temperature, the solvent was removed
under vacuum, and the residue was extracted with pentane (3 × 5 mL).
7 was isolated by crystallization from a CH2Cl2/pentane solution at
1
-30 °C as colorless crystals (0.29 g, 84% yield): mp 95-97 °C; H
NMR (CDCl3, 400 MHz) δ 0.41 (s, 9 H, CH3Si), 1.40 (d, JHH ) 6.8
Hz, 12 H, CH3CHN), 1.43 (d, JHH ) 6.8 Hz, 12 H, CH3CHN), 1.43 (s,
9 H, CH3C), 3.79 (sept d, JPH ) 13.3 Hz, JHH ) 6.8 Hz, 4 H, CH3CHN);
13C NMR (CDCl3, 100.630 MHz) δ 3.22 (s, CH3Si), 23.95 (s, CH3-
CHN), 24.16 (s, CH3CHN), 30.51 (d, JPC ) 4.2 Hz, CH3C), 39.51 (dd,
JPC ) 12.9 and 50.0 Hz, CH3C), 49.16 (d, JPC ) 4.2 Hz, CH3CHN),
141.04 (dd, JPC ) 20.4 and 28.3 Hz, PCSi), 199.90 (dd, JPC ) 78.7
and 105.3 Hz, PCt-Bu); 31P NMR (CDCl3, 32.438 MHz) δ +44.52 (d,
JPP ) 6.7 Hz, PO2), +114.11 (qd, JPH ) 13.3 Hz, JPP ) 6.7 Hz, σ4-P).
Anal. Calcd for C21H46N2O2P2Si: C, 56.22; H, 10.33; N, 6.24.
Found: C, 56.39; H, 10.47; N, 6.39.
(η1-Diphosphete)pentacarbonyltungsten Complex 8. A CH2Cl2
solution (1 mL) of bis(trimethylsilyl)peroxide (0.08 g, 0.43 mmol) was
added dropwise at -78 °C to a CH2Cl2 solution (1 mL) of 3 (0.32 g,
0.43 mmol). The solution was allowed to warm to room temperature,
the solvent was removed under vacuum, and the residue was extracted
with pentane (3 × 5 mL). Complex 8 was isolated as a yellow oil
(0.22 g, 68% yield): 1H NMR (CDCl3, 400 MHz) δ 0.41 (s, 9 H, CH3-
Si), 1.48 (s, 9 H, CH3C), 1.51 (d, JHH ) 6.9 Hz, 12 H, CH3CHN), 1.55
(d, JHH ) 6.9 Hz, 12 H, CH3CHN), 3.71 (sept d, JPH ) 10.9 Hz, JHH
) 6.9 Hz, 2 H, CH3CHN), 4.07 (sept d, JPH ) 10.9 Hz, JHH ) 6.9 Hz,
2 H, CH3CHN); 13C NMR (CDCl3, 100.630 MHz) δ 3.54 (s, CH3Si),
24.08 (d, JPC ) 4.2 Hz, CH3CHN), 24.37 (d, JPC ) 4.0 Hz, CH3CHN),
25.24 (d, JPC ) 2.7 Hz, CH3CHN), 26.19 (s, CH3CHN), 31.33 (dd, JPC
) 2.8 and 2.7 Hz, CH3C), 40.67 (dd, JPC ) 15.0 and 52.1 Hz, CH3C),
48.63 (d, JPC ) 6.4 Hz, CH3CHN), 51.93 (d, JPC ) 3.9 Hz, CH3CHN),
144.62 (dd, JPC ) 7.4 and 13.1 Hz, PCSi), 198.40 (dd, JPC ) 7.3 and
1.1 Hz, JWC ) 127.1 Hz, COe), 201.15 (d, JPC ) 24.9 Hz, COa), 201.38
(dd, JPC ) 1.8 and 48.0 Hz, PCt-Bu); 31P NMR (CDCl3, 162.000 MHz)
δ +72.44 (dq, JPP ) 110.9 Hz, JPH ) 10.9 Hz, σ4-P), +160.80 (d, JPP
) 110.9 Hz, JWP ) 265.0 Hz, PW). Anal. Calcd for C26H46N2O6P2-
SiW: C, 41.27; H, 6.13; N, 3.70. Found: C, 41.01; H, 6.00; N, 3.55.
Cationic 1σ4,2σ5-Diphosphete 9. An ether solution (1 mL) of
TCBQ (0.15 g, 0.61 mmol) was added dropwise, at -78 °C, to an
ether solution (1 mL) of 4 (0.35 g, 0.61 mmol). The mixture was
allowed to warm to room temperature and filtered, and the solvent was
removed under vacuum. 9 was isolated as an orange oil (0.43 g, 86%
yield): 1H NMR (CDCl3, 400 MHz) δ 0.50 (s, 9 H, CH3Si), 1.24 (d,
JHH ) 6.8 Hz, 6 H, CH3CHN), 1.27 (d, JHH ) 6.8 Hz, 6 H, CH3CHN),
1.29 (d, JHH ) 6.8 Hz, 6 H, CH3CHN), 1.32 (d, JHH ) 6.8 Hz, 6 H,
CH3CHN), 1.55 (s, 9 H, CH3C), 2.30 (dd, JPH ) 8.6 and 7.6 Hz, 3 H,
PCH3), 3.73 (sept d, JPH ) 10.0 Hz, JHH ) 6.8 Hz, 2 H, CH3CHN),
3.91 (sept d, JPH ) 13.6 Hz, JHH ) 6.8 Hz, 2 H, CH3CHN); 13C NMR
(CDCl3, 100.630 MHz) δ 2.92 (dd, JPC ) 2.1 and 1.9 Hz, CH3Si),
20.94 (dd, JPC ) 66.1 and 4.0 Hz, PCH3), 24.52 (m, CH3CHN), 25.02
(dd, JPC ) 3.6 and 2.1 Hz, CH3CHN), 25.93 (dd, JPC ) 2.1 and 1.9
Hz, CH3CHN), 31.33 (dd, JPC ) 2.1 and 1.5 Hz, CH3C), 41.53 (dd,
JPC ) 9.3 and 51.9 Hz, CH3C), 50.14 (dd, JPC ) 8.0 and 1.9 Hz,
CH3CHN), 52.64 (d, JPC ) 3.6 Hz, CH3CHN), 115.24 (dd, JPC ) 6.6
and 4.2 Hz, OCC), 116.54 (d, JPC ) 12.3 Hz, OCC), 120.20 (qua, JFC
) 319.6 Hz, CF3), 124.29 (s, OCCC), 127.36 (s, OCCC), 138.28 (d,
JPC ) 2.5 Hz, OC), 142.17 (dd, JPC ) 26.5 and 44.2 Hz, PCSi), 144.24
(dd, JPC ) 4.0 and 8.5 Hz, OC), 209.92 (dd, JPC ) 7.6 and 85.0 Hz,
PCt-Bu); 31P NMR (CDCl3, 81.015 MHz) δ +25.24 (dqua, JPP ) 35.8
Hz, JPH ) 8.6 Hz, σ5-P), +117.00 (m, JPP ) 35.8 Hz, σ4-P). Anal.
Hz, PCSi), 142.77 (dd, JPC ) 4.3 and 4.7 Hz, OC), 142.80 (d, JPC
)
1.0 Hz, OC), 143.02 (d, JPC ) 4.2 Hz, OC), 144.99 (d, JPC ) 3.4 Hz,
OC), 207.04 (dd, JPC ) 89.1 and 120.4 Hz, PCt-Bu); 31P NMR (CDCl3,
81.015 MHz) δ -65.45 (d, JPP ) 122.1 Hz, PO4), +131.28 (dq, JPP
)
122.1 Hz, JPH ) 9.0 Hz, σ4-P). Anal. Calcd for C33H46N2Cl8O4P2Si:
C, 43.63; H, 5.10; N, 3.08. Found: C, 43.72; H, 5.24; N, 3.00.
(η1-Diphosphete)pentacarbonyltungsten Complex 11. A THF
solution (2 mL) of TCBQ (0.80 g, 0.41 mmol) was added dropwise, at
-78 °C, to a THF solution (1 mL) of 3 (0.30 g, 0.41 mmol). The
solution was allowed to warm to room temperature and filtered, and
the solvent was removed under vacuum. The residue was extracted
with ether (3 × 5 mL), and 11 was isolated by crystallization from a
CH2Cl2 solution at -30 °C as pale yellow crystals (0.36 g, 88%
1
yield): mp 91 °C dec; H NMR (CDCl3, 400 MHz) δ 0.45 (s, 9 H,
CH3Si), 1.20-1.35 (m, 24 H, CH3CHN), 1.31 (s, 9 H, CH3C), 3.50-
4.00 (m, 4 H, CH3CHN); 13C NMR (CDCl3, 100.630 MHz) δ 3.44 (s,
CH3Si), 24.86 (d, JPC ) 4.5 Hz, CH3CHN), 24.95 (dd, JPC ) 2.2 and
2.3 Hz, CH3CHN), 25.68 (d, JPC ) 3.2 Hz, CH3CHN), 26.91 (s, CH3-
CHN), 31.93 (d, JPC ) 2.1 Hz, CH3C), 40.73 (dd, JPC ) 10.6 and 55.1
Hz, CH3C), 49.80 (dd, JPC ) 8.7 and 2.1 Hz, CH3CHN), 52.37 (s,
CH3CHN), 114.58 (dd, JPC ) 6.4 and 1.8 Hz, OCC), 115.87 (d, JPC
)
8.6 Hz, OCC), 124.78 (s, OCCC), 125.25 (s, OCCC), 130.00 (dd, JPC
) 27.0 and 40.4 Hz, PCSi), 140.86 (dd, JPC ) 2.1 and 2.1 Hz, OC),
149.77 (d, JPC ) 6.8 Hz, OC), 198.31 (d, JPC ) 8.1 Hz, JWC ) 127.5
Hz, COe), 199.62 (d, JPC ) 34.5 Hz, COa), 215.43 (dd, JPC ) 41.9 and
73.6 Hz, PCt-Bu); 31P NMR (CDCl3, 161.986 MHz) δ +74.32 (JPP
25.1 Hz, JWP ) 299.3 Hz, PW), +80.42 (dq, JPP ) 25.1 Hz, JPH
)
)
12.3 Hz, σ4-P). Anal. Calcd for C32H46N2Cl4O7P2SiW: C, 38.96; H
4.70; N, 2.84. Found: C, 39.09; H, 4.78; N, 2.89.
Zwitterionic 1σ4,2σ3-Diphosphete 12. A toluene solution (0.4 mL)
of trimethylphosphine (0.40 mmol) was added dropwise, at -78 °C,
to a THF solution (1 mL) of 11 (0.20 g, 0.20 mmol). The solution
was allowed to warm to room temperature and stirred for 12 h at room
temperature. The solvent and excess trimethylphosphine were removed
under vacuum, and the residue was extracted with pentane (3 × 5 mL).
12 was isolated by crystallization from an ether solution at -30 °C as
1
pale yellow crystals (0.05 g, 46% yield): mp 121-123 °C dec; H
NMR (CDCl3, 400 MHz, 293 K) δ 0.42 (s, 9 H, CH3Si), 1.31 (d, JHH
) 6.9 Hz, 6 H, CH3CHN), 1.39 (d, JHH ) 6.9 Hz, 6 H, CH3CHN),
1.44 (d, JHH ) 6.9 Hz, 6 H, CH3CHN), 1.44 (s, 9 H, CH3C), 1.51 (d,
JHH ) 6.9 Hz, 6 H, CH3CHN), 3.98 (sept d, JPH ) 10.0 Hz, JHH ) 6.9
Hz, 4 H, CH3CHN); 13C NMR (CDCl3, 100.630 MHz, 293K) δ 1.64
(s, CH3Si), 23.45 (d, JPC ) 2.6 Hz, CH3CHN), 23.51 (d, JPC ) 2.6 Hz,
CH3CHN), 23.75 (dd, JPC ) 2.4 Hz, CH3CHN), 23.77 (d, JPC ) 2.4
Hz, CH3CHN), 24.44 (d, JPC ) 2.8 Hz, CH3CHN), 25.14 (d, JPC ) 3.9
Hz, CH3CHN), 29.67 (dd, JPC ) 4.3 and 1.4 Hz, CH3C), 39.43 (dd,
JPC ) 13.7 and 47.9 Hz, CH3C), 47.76 (d, JPC ) 5.4 Hz, CH3CHN),
47.82 (d, JPC ) 5.4 Hz, CH3CHN), 51.83 (d, JPC ) 4.3 Hz, CH3CHN),
the other carbon atoms are not observed. 31P NMR (CDCl3, 161.990