Article
Inorganic Chemistry, Vol. 48, No. 19, 2009 9465
1J(107Ag-P) = 571 Hz, 1J(109Ag-P) = 662 Hz) ppm. IR (KBr,
cm-1): 2105 (ν SdCdN, vs) cm-1. Melting Point: 197-198 °C.
Anal. Calcd for C38H66Ag2N2P2S2: C, 51.12; H, 7.45; N; 3.14.
Found: C, 50.85; H, 7.48; N; 3.10.
toluene was removed by rotary evaporation, the white solid
washed with pentane, and the solid collected and dried. The
solution phase chemical shifts and 1J(107/109Ag-P) coupling
constants for 31P{1H} NMR spectra of 9 matched the values
in reference 9. Yield: 87 mg (92%). Anal. Calcd for C36H66-
Ag2Br2P2: C, 46.18; H, 7.10. Found: C, 46.27; H, 6.89.
[(PCy3)Ag(μ-(1,2,4-triazol-1-yl)]2 (5). In 5 mL of toluene, 1
(118 mg, 0.26 mmol) was dissolved and under an inert atmo-
sphere, ∼1.05 equiv of 1-trimethylsilyl(1,2,4-triazole) (0.04 mL,
0.28 mmol) was added via syringe. After 6 h, cesium carbonate
(201 mg, 0.62 mmol) was added, and the suspension stirred for 1
h. The suspension was filtered through potassium carbonate,
and the filtrate collected. The toluene was removed by rotary
evaporation, the residue triturated with pentane, the white solid
collected, washed with ether, and dried. Yield: 107 mg (89%). 1H
NMR: δ 8.07 (s, 4H, C2N3H2), 1.18-2.05 (m, 66H, P(C6H11)3)
ppm. 31P{1H} NMR: δ 38.4 (dd, 1J(107Ag-P) = 558 Hz,
1J(109Ag-P) = 645 Hz) ppm. Melting Point: 165-167 °C. Anal.
Calcd for C40H70Ag2N6P2: C, 52.62; H, 7.73; N, 9.20. Found: C,
52.38; H, 7.49; N, 9.32.
[(IPr)Ag(OAc)] (10). In 5 mL of dichloromethane, 12
(prepared in large scale from reference 6d, 332 mg, 0.62 mmol)
was dissolved. Silver(I) acetate (1.06 equiv, 110 mg, 0.66 mmol)
was added, and the flask covered with aluminum foil. Under
argon, thesuspensionwasstirredfor2 h, filteredthroughCelite(in
air), and the solvent removed by rotary evaporation. The residue
was triturated with pentane and dried, extracted into toluene, and
filtered through Celite. The toluene was removed by rotary
evaporation, and the colorless solid triturated with pentane. The
resultant colorless solid was collected and dried. Yield: 300 mg
(86%). 1H NMR: δ 7.50 (t, 2H, para-C6H3(CH(CH3)2)2, J = 7.6
Hz), 7.30 (d, 4H, meta-C6H3(CH(CH3)2)2, J = 7.6 Hz), 7.23 (s,
2H, vinyl CH), 2.56 (sep, 4H, C6H3(CH(CH3)2)2, J = 6.8 Hz),
1.85 (s, 3H, O2CCH3), 1.30 (d, 12H, C6H3(CH(CH3)2)2, J = 6.8
Hz), 1.23 (d, 12H, C6H3(CH(CH3)2)2, J = 6.8 Hz) ppm. 13C
NMR: δ 184.32 (dd, Ccarbene, J(107/109Ag/13C) = 249, 286 Hz),
178.05 (s, O2CCH3), 145.53 (s), 134.60 (s), 130.51 (s), 124.17 (s),
123.42 (d, vinyl carbon, J = 8.3 Hz), 28.62 (s), 24.59 (s), 23.92 (s),
22.58 (s) ppm. Melting Point: 200 °C (dec.). Anal. Calcd for
C29H39AgN2O2: C, 62.50; H, 7.08; N, 5.04. Found: C, 62.70; H,
7.11; N, 4.99.
[(PCy3)Ag(μ-OTf)]2 (6). In 4 mL of toluene, 1 (97 mg, 0.22
mmol) was dissolved and (in a glovebox freezer) cooled to
-20 °C. Separately, ∼1.2 equiv of trimethylsilyltrifluorometha-
nesulfonate (58 mg, 0.26 mmol) in 2 mL of toluene was cooled in
a glovebox freezer to the same temperature. The two solutions
were removed from the freezer, and the trimethylsilyltrifluor-
omethanesulfonate solution was added dropwise to the solu-
tion of 1. After 1.5 h, the product solution was taken to dry-
ness via rotary evaporation, and the residue triturated with
pentane. The dry, crude solid was dissolved in a minimum of
benzene, and pentane vapor was diffused into the saturated
benzene solution, causing separation of a colorless, crystalline
solid that was dried and collected. Yield: 85 mg (73%). 1H
NMR: δ 1.17-1.96 (m, 66H, P(C6H11)3) ppm. 19F NMR: δ
-77.58 ppm. 31P{1H} NMR: δ 47.1 (br d) ppm. IR (KBr, cm-1):
1321, 1188, 994 (vs) cm-1. Melting Point: 171-172 °C. Anal.
Calcd for C38H66Ag2F6O6P2S2: C, 42.47; H, 6.19. Found: C,
42.43; H, 5.92.
[(IPr)Ag(N3)] (11). In 5 mL of toluene, 10 (80 mg, 0.14 mmol)
was dissolved in a round-bottom flask (fitted with a rubber
septum), and trimethylsilylazide (2 equiv, 0.04 mL, 0.30 mmol)
was added via syringe. The solution became cloudy and was
stirred for 6 h. The toluene was removed by rotary evaporation,
and the solid was triturated with pentane. The spectroscopically
and analytically pure white solid was collected and dried. Yield:
74 mg (95%). 1H NMR: δ 7.52 (t, 2H, para-C6H3(CH(CH3)2)2,
J = 8.0 Hz), 7.31 (d, 4H, meta-C6H3(CH(CH3)2)2, J = 7.6 Hz),
7.24 (s, 2H, vinyl CH), 2.52 (sep, 4H, C6H3(CH(CH3)2)2, J =
6.8Hz), 1.26(d, 12H, C6H3(CH(CH3)2)2, J=6.8Hz), 1.23(d, 12H,
C6H3(CH(CH3)2)2, J = 6.8 Hz) ppm. 13C NMR: δ 183.04
(dd, Ccarbene, J(107/109Ag/13C) = 237, 273 Hz), 145.36 (s),
134.28 (s), 130.69 (s), 124.26 (s), 123.65 (d, vinyl carbon, J =
7.5 Hz), 28.56 (s), 24.53 (s), 23.88 (s) ppm. IR (KBr, cm-1): 2038
(νas NdNdN, vs), 1326 (νs NdNdN, m) cm-1. Anal. Calcd for
C27H36AgN5: C, 60.22; H, 6.74; N; 13.01. Found: C, 60.24; H,
6.90; N; 12.91.
[(PCy3)Ag(pyr)](OTf) (7). Compound 6 (63 mg, 0.059 mmol)
was dissolved in a minimum of pyridine (low-water content,
Acros) and pentane vapor was diffused into the saturated
pyridine solution, causing separation of colorless crystals which
1
were analytically pure upon drying. Yield: 55 mg (76%). H
NMR: δ 8.66-8.70 (2H, m, C5H5N), 7.82 (tt, 1H, para-C5H5N,
J = 1.6, 8.0 Hz), 7.41-7.46 (m, 2H, C5H5N), 1.02-2.02 (m,
33H, P(C6H11)3) ppm. 19F NMR: δ -78.43 ppm. 31P{1H}
NMR: δ 42.9 (dd, 1J(107Ag-P) = 599 Hz, 1J(109Ag-P) = 692
Hz) ppm. IR (KBr, cm-1): 1281, 1251, 1027 (vs) cm-1. Anal.
Calcd for C24H38AgF3NO3PS: C, 46.76; H, 6.21; N, 2.27.
Found: C, 46.51; H, 6.02; N, 2.24.
[(IPr)AgCl] (12). This compound has been prepared pre-
viously, but using different methodology.6d In a glovebox, in 3
mL of toluene, 10 (52 mg, 0.094 mmol) was dissolved. A solution
of chlorotrimethylsilane (1.2 equiv, 12 mg, 0.11 mmol) in 1 mL
of toluene was added dropwise, and the solution stirred for 6 h.
Toluene was removed by rotary evaporation, and the colorless
solid was triturated with pentane. The resultant solid was
collected and dried. Yield: 48 mg (96%). Anal. Calcd for
C27H36AgClN2: C, 60.97; H, 6.82; N; 5.27. Found: C, 60.73;
H, 6.74; N; 5.00.
[(PCy3)Ag(SPh)]n (8). In 4 mL of toluene, 1 (95 mg, 0.21
mmol) was dissolved. Under an inert atmosphere,
(phenylthio)trimethylsilane (47 mg, 0.26 mmol) was added,
and the solution was stirred for 6 h. The toluene was removed
via rotary evaporation, and pentane was added. The pentane
was removed by rotary evaporation, and methanol was added to
cause separation of a sticky white (pentane soluble) precipitate
which was collected and dried under vacuum. A foamy white
solid was collected. Yield: 65 mg (62%). 1H NMR: δ 7.51 (2H, d,
ortho-C6H5S, J = 7.2 Hz), 6.97 (t, 2H, meta-C6H5S, J = 7.6 Hz),
6.86 (t, 1H, para-C6H5S, J = 7.2 Hz), 1.05-1.98 (m, 33H,
P(C6H11)3) ppm. 13C NMR: δ 144.76 (s), 133.22 (s), 127.45 (s),
122.00 (s), 32.00 (d, 1JC-P = 12.3 Hz), 30.82 (d, JC-P = 4.6 Hz),
27.25 (d, JC-P = 11.4 Hz), 25.93 (s) ppm. 31P{1H} NMR (243 K,
only one doublet resolved): δ 35.5 (d) ppm. Anal. Calcd for
C24H38AgPS: C, 57.94; H, 7.70. Found: C, 57.88; H, 7.49.
[(PCy3)Ag(μ-Br)]2 (9). This compound has been prepared
previously,9 but using different methodology. In 4 mL of
toluene, 1 (90 mg, 0.20 mmol) was dissolved and under an inert
atmosphere, 1 equiv of bromotrimethylsilane (31 mg, 0.20
mmol) in 2 mL of toluene was added dropwise. After 6 h, the
[(IPr)AgBr] (13). In 10 mL of dichloromethane, 12 (70 mg,
0.13 mmol) was dissolved. A 10 mL aqueous solution of KBr
(5.5 equiv, 86 mg, 0.72 mmol) was added, and the resultant
biphasic mixture was vigorously stirred for 4 h. The organic
phase was segregated, and the aqueous phase was washed once
with 10 mL of dichloromethane. The organic phases were
combined and washed twice with 10 mL of distilled water, dried
with MgSO4, and filtered through Celite. The filtrate was
reduced to dryness via rotary evaporation, and the resultant
residue was triturated with pentane to cause separation of a
colorless solid, which was collected and dried. Yield: 54 mg
(71%). 1H NMR: δ 7.48 (t, 2H, para-C6H3(CH(CH3)2)2, J = 7.6
Hz), 7.28 (d, 4H, meta-C6H3(CH(CH3)2)2, J = 7.6 Hz), 7.21 (d,
2H, vinyl CH, J = 1.6 Hz), 2.53 (sep, 4H, C6H3(CH(CH3)2)2,