Borecki and Corrigan
stirring. Storage of the product at -80 °C resulted in the formation
of low-melting-point crystals. Yield: 86%, 1.0 g. Mp: -28 °C.
1H NMR (CD2Cl2, -60 °C): δ 7.25 (s, Ph, 15H), 1.66 (s, CH2,
12H), 0.75 (s, CH2CH3, 18H), 0.34 (s, SiMe3, 9H). 13C{1H} NMR
(CD2Cl2, -60 °C): δ 136.0 (s, CPh), 130.2-127.4 (CPh), 16.7 (s,
CH2), 7.6 (s, CH2CH3), 7.3 (s, SiMe3). 31P{1H} NMR (CD2Cl2,
-60 °C): δ -12.8 (br s, W1/2 ) 133 Hz). 29Si NMR (CD2Cl2, -60
°C): δ +0.8. 77Se{1H} NMR (CD2Cl2, -60 °C): δ -546 (br s,
W1/2 ) 93 Hz).
Synthesis of (EtPh2P)3CuSeSiMe3 (2b). CuOAc (0.22 g, 1.8
mmol) was dissolved with 4 equiv of PPh2Et (1.48 mL, 7.2 mmol)
in 3 mL of CHCl3 and 1 mL of hexane. The clear, colorless solution
was cooled to -60 °C, and Se(SiMe3)2 (0.40 mL, 1.8 mmol) was
added. The solution was gradually warmed to -10 °C and
subsequently placed at -80 °C. Colorless, blocklike crystals
precipitated after 4 days. Yield: 96%, 1.5 g. Mp: -15 °C. 1H NMR
(CD2Cl2, -60 °C): δ 7.28 (s, Ph, 30H), 7.10 (s, Ph, 30H), 6.80 (s,
Ph, 30H), 2.19 (br s, CH2, 6H), 0.68 (br s, CH2CH3, 9H), 0.54 (s,
SiMe3, 9H). 13C{1H} NMR (CD2Cl2, -60 °C): δ 138.3 (s, CPh),
132.8-127.7 (CPh), 20.0 (s, CH2), 9.7 (s, CH2CH3), 7.3 (s, SiMe3).
31P{1H} NMR (CD2Cl2, -60 °C): δ -5.6 (br s, W1/2 ) 361 Hz).
29Si NMR (CD2Cl2, -60 °C): δ +2.4. 77Se{1H} NMR (CD2Cl2,
-60 °C): δ -527 (br s, W1/2 ) 90 Hz).
°C): δ 134.2 (CPh), 131.2-128.8 (CPh), 18.0 (s, CH2), 8.3 (s,
CH2CH3), 7.0 (s, SiMe3). 29Si NMR (CD2Cl2, -70 °C): δ 7.9. 31P-
{1H} NMR (CD2Cl2, -80 °C): δ -4.3 (br s, W1/2 ) 64 Hz).
Synthesis of (EtPh2P)3AgSSiMe3 (4b). AgOAc (0.2 g, 1.2
mmol) was dissolved in 5 mL of Et2O with the addition of 4 equiv
of PPh2Et (1.00 mL, 4.85 mmol). The resulting solution was cooled
to -70 °C, and a white solid appeared. The solid dissolved with
the addition of 1 equiv of S(SiMe3)2 (0.25 mL, 1.2 mmol), and the
reaction was stirred for an additional 60 min. 4b precipitated out
as a white solid with the addition of cold hexane at -80 °C. The
low-melting-point solid was isolated, washed with hexane, and dried
1
under vacuum. Yield: 92%, 1.0 g. Mp: -25 °C. H NMR (CD2-
Cl2, -70 °C): δ 7.28-7.20 (m, Ph, 30H), 2.02 (s, CH2, 6H), 0.88
(s, CH2CH3, 9H), 0.19 (s, SiMe3, 9H). 13C{1H} NMR (CD2Cl2,
-70 °C): δ 135.3 (s, CPh), 132.8-128.4 (CPh), 20.1 (s, CH2), 9.0
(s, CH2CH3), 7.2 (s, SiMe3). 31P{1H} NMR (CD2Cl2, -70 °C): δ
-0.8 (br s, W1/2 ) 136 Hz). 29Si{1H} NMR (CD2Cl2, -70 °C): δ
8.7.
Synthesis of (Et2PhP)3AgSeSiMe3 (5a). AgOAc (0.12 g, 0.719
mmol) and 4 equiv of PEt2Ph (0.50 mL, 2. 876 mmol) were placed
in 5 mL of diethyl ether. The clear colorless solution was cooled
to ∼-70 °C, and 1 equiv of Se(SiMe3)2 was added with stirring.
The resulting clear and colorless solution was stirred for an
additional 60 min during warming to ∼-40 °C. The product was
precipitated with the addition of cold hexane and storage at -80
°C. A white solid was isolated, washed with hexane, and dried under
Synthesis of (Et2PhP)3CuTeSiMe3 (3a). CuOAc (0.13 g, 1.1
mmol) was dissolved with 4 equiv of PEt2Ph (0.74 mL, 4.3 mmol)
in 5 mL of Et2O and cooled to -60 °C. Te(SiMe3)2 was added,
and the reaction was stirred for an additional 60 min. Half of the
solvent was removed under vacuum, and the resulting white product
precipitated with the addition of cold hexane. The isolated solid
was washed with hexane and dried under vacuum. Yield: 94.8%,
1
vacuum. Yield: 58%, 0.55 g. Mp: -50 °C. H NMR (CD2Cl2,
-70 °C): δ 7.42 (s, Ph, 6H), 7.27 (s, Ph, 9H), 1.65 (s, CH2, 12H),
0.81 (s, CH2CH3, 18H), 0.25 (s, SiMe3, 9H). 13C{1H) NMR (CD2-
Cl2, -70 °C): δ 135.6 (s, CPh), 130.9-127.5 (CPh), 18.1 (t, JPC
)
1
0.8 g. Mp: -47 °C. H NMR (CD2Cl2, -60 °C): δ 7.22 (s, Ph,
22 Hz, CH2), 8.4 (s, CH2CH3), 7.4 (s, SiMe3). 31P{1H} NMR (CD2-
Cl2, -70 °C): δ -9.4 (br s, W1/2 ) 197 Hz). 29Si NMR (CD2Cl2,
-70 °C): δ 0.8. 77Se{1H} NMR (CD2Cl2, -70 °C): δ -559 (br
s, W1/2 ) 47 Hz).
15H), 1.65 (s, CH2, 12H), 0.70 (s, CH3, 18H), 0.49 (s, TeSiMe3,
9H). 13C{1H} NMR (CD2Cl2, -60 °C): δ 135.7 (s, CPh), 130.5 (s,
CPh), 127.8 (s, CPh), 17.1 (s, CH2), 7.8 (s, CH2CH3), 7.6 (s, SiMe3).
31P{1H} NMR (CD2Cl2, -60 °C): δ -12.7 (br, W1/2 ) 56 Hz).
29Si NMR (CD2Cl2, -60 °C): δ -22.0. 125Te{1H} NMR (CD2Cl2,
Synthesis of (EtPh2P)3AgSeSiMe3 (5b). AgOAc (0.2 g, 1.2
mmol) was dissolved in 4 mL of dry Et2O with the addition of 4
equiv of PPh2Et (1.0 mL, 4.9 mmol). Upon cooling of the clear
colorless solution to -70 °C, a white precipitate formed and was
redissolved with the addition of Se(SiMe3)2 (0.26 mL, 1.2 mmol).
After stirring for ∼1 h, a white, low-melting-point solid was
precipitated with the addition of cold hexane. The product was
isolated, washed with hexane, and dried under vacuum. Yield: 96%,
1.0 g. Mp: -35 °C (dec). 1H NMR (CD2Cl2, -70 °C): δ 7.29 (s,
Ph, 8H), 7.19 (s, Ph, 22H), 1.98 (s, CH2, 6H), 0.85 (t, JHH ) 6 Hz,
CH2CH3, 9H), 0.34 (s, SiMe3, 9H). 13C{1H} NMR (CD2Cl2, -70
°C): δ 134.8 (s, CPh), 132.76-128.32 (CPh), 20.2 (s, CH2), 8.9 (s,
CH2CH3), 7.4 (s, SiMe3). 31P{1H} NMR (CD2Cl2, -70 °C): δ -3.1
(br s, W1/2 ) 172 Hz). 29Si NMR (CD2Cl2, -70 °C): δ 0.1. 77Se-
{1H} NMR (CD2Cl2, -70 °C): δ -549 (br s, W1/2 ) 54 Hz).
Synthesis of (PEt2Ph)3CuSeH (6). CuOAc (0.24 g, 2.0 mmol)
was dissolved with 4 equiv of PEt2Ph (1.38 mL, 7.9 mmol) in 8
mL of Et2O. The solution was cooled to -60 °C, and Se(SiMe3)2
(0.42 mL, 2.0 mmol) was added. The reaction was stirred for 2 h
with warming to ∼-10 °C, and a few drops of ethanol was added.
The solution was cooled to -80 °C. Colorless blocklike crystals
2
-60 °C): δ -1259 (q, JTeP ) 92 Hz).
Synthesis of (EtPh2P)3CuTeSiMe3 (3b). CuOAc (0.20 g, 1.6
mmol) was placed in a flask with 2 mL of CH2Cl2 and 5 mL of
hexane. The suspension was dissolved with the addition of 4 equiv
of PPh2Et (1.35 mL, 6.6 mmol). The clear colorless solution was
cooled to -60 °C, and Te(SiMe3)2 (0.35 mL, 1.6 mmol) was added.
The reaction turned a slight orange color as it was warmed to -40
°C and stirred for ∼2 h. Storage at -80 °C for a few days led to
cube-shaped crystals of 3b. Yield: 95.8%, 1.4 g. Mp: -25 °C. 1H
NMR (CD2Cl2, -60 °C): δ 7.04 (t, JHH ) 7 Hz, Ph, 15H), 6.72 (s,
Ph, 3H), 6.62 (s, Ph, 12H), 2.16 (s, CH2, 6H), 0.54 (s, CH2CH3,
9H), 0.60 (s, SiMe3, 9H). 13C{1H} NMR (CD2Cl2, -60 °C): δ
132.1 (s, CPh), 128.1 (s, CPh), 127.6 (s, CPh), 20.5 (s, CH2), 7.3
(s,CH2CH3), 7.6 (s, SiMe3). 31P{1H} NMR (CD2Cl2, -60 °C): δ
-5.2 (br, W1/2 ) 131 Hz). 29Si NMR (CD2Cl2, -60 °C): δ -20.6.
125Te{1H} NMR (CD2Cl2, -60 °C): δ -1229 (q, 2JTeP ) 94 Hz).
Synthesis of (Et2PhP)3AgSSiMe3 (4a). AgOAc (0.20 g, 1.2
mmol) and 4 equiv of PEt2Ph (0.83 mL, 4.8 mmol) were placed in
4 mL of dry Et2O to yield a clear colorless solution. The solution
was cooled to ∼-70 °C, and 1 equiv of S(SiMe3)2 (0.25 mL, 1.2
mmol) was added while the reaction was stirred. The solution
remained colorless and was warmed slowly to ∼-25 °C. The pure
complex was precipitated out of the solution with cold hexane and
isolated as a low-melting-point colorless solid. Yield: 58%, 0.50
g. Mp: -40 °C (dec). 1H NMR (CD2Cl2, -70 °C): δ 7.46 (s, Ph,
6H), 7.29 (t, J ) 7 Hz, Ph, 9H), 1.71 (s, CH2, 12H), 0.82 (s,
CH2CH3, 18H), 0.10 (s, SiMe3, 9H). 13C{1H} NMR (CD2Cl2, -70
1
of 6 precipitated over 12 h. Yield: 88%, 1.12 g. H NMR (CD2-
Cl2, -30 °C): δ 7.34 (s, Ph, 6H), 7.24 (s, Ph, 9H), 1.62 (q, JHH
)
7 Hz, CH2, 12H), 0.74 (t, JHH ) 7 Hz, CH3, 18H), -5.26 (s, 1H,
JSeH ) 13 Hz). 13C{1H} NMR (CD2Cl2, -30 °C): δ 136.4 (s, CPh),
130.9 (s, CPh), 128.0 (s, CPh), 17.2 (d, JPC ) 22 Hz, CH2), 7.8 (s,
CH3). 31P{1H} NMR (CD2Cl2, -30 °C): δ -11.0 (br s, W1/2
327 Hz). 77Se{1H} NMR (CD2Cl2, -30 °C): δ -507 (br s, W1/2
108 Hz).
)
)
2480 Inorganic Chemistry, Vol. 46, No. 7, 2007