5342 Organometallics, Vol. 22, No. 25, 2003
Djordjevic et al.
(3.55) [L]+. Anal. Calcd for C31H26AuO2PS‚0.3C5H12 (712.19):
C, 54.8; H, 4.19. Found: C, 54.6; H, 4.11.
chloroform/n-pentane on cooling to -10 °C. NMR spectra were
obtained in CD2Cl2 at 25 °C. 31P NMR: 37.3 (s). 13C NMR:
116.6 (t, 2J (PC) ) 75, Au2C), 134.6 (d, J ) 15), 131.9 (s), 130.4
(d, J ) 55), and 129.5 (d, J ) 12) for o-, p-, i-, and m-C of PhP;
132.8, 131.0, 128.8, and 128.1, all s, for i-, p-, m-, and o-C of
PhS. 1H NMR: 7.24-8.18 (m, 30 H, Ph). MS (FAB): m/z 1212
(14.05) [M]+, 720 (47.19) [L2Au]+, 459 (100) [LAu]+. Anal. Calcd
for C49H40Au2O4P2S2‚0.15CHCl3 (1230.76): C, 47.96; H, 3.28.
Found: C, 47.74; H, 3.59.
[(Tr ip h en ylp h osp h in e)gold ]m eth ylen ebis(p h en yl su l-
fon e). PhSO2CH2SO2Ph (89 mg, 0.3 mmol) was dissolved in
tetrahydrofuran (10 mL) and treated with 0.19 mL of a 1.6 M
solution of nBuLi in hexanes at -78 °C. After the mixture was
stirred for 2 h, a solution of Ph3PAuCl (150 mg, 0.3 mmol) in
20 mL of tetrahydrofuran was added. The stirred reaction
mixture was warmed to room temperature overnight. The
solvents were evaporated, the residue was extracted with CH2-
Cl2, and the solvent was again evaporated under vacuum. The
residue was washed with pentane and diethyl ether and dried
under vacuum: 196 mg (87% yield); mp 186 °C dec. Single
crystals were grown from dichloromethane/n-pentane on cool-
ing to -10 °C. NMR spectra were obtained in CD2Cl2 at 25
°C. 31P NMR: 39.7 (s). 13C NMR: 81.14 (d, J ) 87, CHS); 134.5
(d, J ) 14), 131.7 (s), 129.4 (d, J ) 55), and 129.3 (d, J ) 12)
for o-, p-, i-, and m-C of PhP; 133.9, 131.5, 129.0, and 129.1,
all s, for i-, p-, m-, and o-C of PhS. 1H NMR: 5.53 (d, 3J ) 8.0,
1H, CH); 8.12-6.72 (m, 25H, Ph). MS (FAB): m/z 754 (7.2)
[M]+, 720 (21.45) [L2Au]+, 459 (100) [LAu]+, 262 (3.89) [L]+.
Anal. Calcd for C31H26AuO4PS2 (754.62): C, 49.34; H, 3.47.
Found: C, 48.85; H, 3.74.
(f) R ) P h , L ) P h 2MeP : 74 mg (0.25 mmol) of sulfone,
216 mg (0.50 mmol) of LAuCl, 2 × 20 mL of solvent. Yield:
267 mg (88%). Mp 197 °C dec. Single crystals were grown from
dichloromethane/n-pentane on cooling to -10 °C. NMR spectra
were obtained in CD2Cl2 at 25 °C. 31P NMR: 21.9 (s). 13C
NMR: 14.3 (d, 1J (PC) ) 36.4); 131.1 (d, J ) 14), 131.9 (s), 130.4
(d, J ) 55), and 128.9 (d, J ) 12) for o-, p-, i-, and m-C of PhP;
132.8, 131.0, 128.9, and 128.8, all s, for i-, p-, m-, and o-C of
PhS. 1H NMR: 2.08 (d, 3J (HP) ) 16.5, 6H, Me); 8.18-7.23
(m, 30H, Ph). MS (FAB): m/z 1088 (9.13) [M]+, 596 (45.14)
[L2Au]+, 396 (100) [LAu]+. Anal. Calcd for C39H36Au2O4P2S2‚
0.5C5H12 (1128.40): C, 44.43; H, 3.80. Found: C, 44.39; H, 3.90.
Dir ect Dia u r a tion of Meth ylen ebis(m eth yl su lfon e)
w ith Tr is[(tr ip h en ylp h osp h in e)gold ]oxon iu m Tetr a flu o-
r obor a te. A solution of MeSO2CH2SO2Me (10 mg, 0.06 mmol)
and potassium carbonate (17 mg, 0.12 mmol) in tetrahydro-
furan (10 mL) and water (2 mL) was added to a suspension of
tris[(triphenylphosphine)gold]oxonium tetrafluoroborate (86
mg, 0.06 mmol) in tetrahydrofuran (10 mL). The mixture was
stirred for 1 day at room temperature. Subsequently, the
solvent was removed under reduced pressure and the product
extracted from the residue with dichloromethane. Following
removal of the dichloromethane, the product was re-extracted
with tetrahydrofuran. The solvent was evaporated, and the
product was washed with n-pentane and dried under vacuum.
Yield: 29.4 mg (45%).
Bis[(tr ip h en ylp h osp h in e)gold ]-, Bis[(tr ip h en yla r sin e)-
gold ]-, a n d Bis[(d ip h en ylm eth ylp h osp h in e)gold ]m eth yl-
en ebis(m eth yl su lfon e) a n d Bis[(tr ip h en ylp h osp h in e)-
gold ]- a n d Bis[(d ip h en ylm eth ylp h osp h in e)gold ]m eth -
ylen ebis(p h en yl su lfon e) by Lith ia tion of th e Su lfon es.
(a ) Gen er a l P r oced u r e. RSO2CH2SO2R was lithiated with
n
2 equiv of BuLi in tetrahydrofuran at -78 °C, and after 2 h
of stirring it was treated with 2 equiv of the (L)AuCl compon-
ent also dissolved in tetrahydrofuran. Evaporation of the
solvent, extraction of the residue with dichloromethane, and
removal of this solvent under vacuum yielded the products,
which were washed with n-pentane or diethyl ether and dried
under vacuum.
Au r a tion of Cya n om eth yl P h en yl Su lfon e. The proce-
dure for the diauration was the same as that for the disulfones,
using 45.7 mg (0.25 mmol) of PhSO2CH2CN and 250 mg (0.5
mmol) of Ph3PAuCl in 2 × 20 mL of tetrahydrofuran: yield
244 mg (89%) of bis[(triphenylphosphine)gold]cyanomethyl
phenyl sulfone; mp 188 °C dec. Single crystals were grown from
dichloromethane/n-pentane on cooling to -10 °C. NMR spectra
were obtained in CD2Cl2 at 25 °C. 31P NMR: 37.9 (s). 13C
NMR: 124.9 (s, CN); 134.6 (d, J ) 13.5), 132.4 (s), 130.2 (d, J
) 55.5), and 129.6 (d, J ) 12) for o-, p-, i-, and m-C of PhP;
135.8, 133.4, 128.8, and 127.6, all s, for i-, p-, m-, and o-C of
PhS. 1H NMR: 8.15-7.33 (m, Ph). MS (FAB): m/z 1097 (8.08)
(b) R ) Me, L ) P h 3P : 43.5 mg (0.25 mmol) of sulfone,
250 mg (0.5 mmol) of LAuCl, 2 × 20 mL of solvent. Yield: 244
mg (90%). Mp: 179 °C dec. Single crystals were grown from
dichloromethane/n-pentane on cooling to -10 °C. NMR spectra
were obtained in CD2Cl2 at 25 °C. 31P NMR: 37.1 (s). 13C
NMR: 48.5 (s, Me); 134.5 (d, J ) 13.5), 131.9 (s), 131.1 (d, J
) 54.5), and 129.5 (d, J ) 10.9) for o-, p-, i-, and m-C of Ph. 1H
NMR: 3.23 (s, 6H, Me); 7.15-7.90 (m, 30H, Ph). MS (FAB):
m/z 1088 (3.07) [M]+, 720 (88.49) [L2Au]+, 459 (100) [LAu]+,
262 (4.19) [L]+. Anal. Calcd for C39H36Au2O4P2S2 (1088.72): C,
43.02; H, 3.33. Found: C, 42.17; H, 3.21.
(c) R ) Me, L ) P h 3As: 32.0 mg (0.18 mmol) of sulfone,
200 mg (0.37 mmol) of LAuCl, 2 × 20 mL of solvent. Yield:
194 mg (89%). Mp: 188 °C dec. Single crystals were grown from
dichloromethane/n-pentane on cooling to -10 °C. NMR spectra
were obtained in CD2Cl2 at 25 °C. 13C NMR: 48.78 (s, Me);
133.79, 131.06, 130.05, and 129.75, all s, for o-, p-, i-, and m-C
of Ph. 1H NMR: 3.29 (s, 6H, Me); 7.51-7.39 (m, 30H, Ph). MS
(FAB): m/z 1176 (14.01) [M]+, 809 (100) [L2Au]+, 503 (62.31)
[LAu]+.
[M]+, 720 (47.65) [L2Au]+, 459 (100) [LAu]+. IR: 2139 cm-1
.
Anal. Calcd for C44H35Au2NO2P2S‚0.5C5H12 (1141.00): C, 49.26;
H, 3.64. Found: C, 49.67; H, 3.82.
A 120 mg portion (0.11 mmol) of this diauration product,
dissolved in 20 mL of tetrahydrofuran at -78 °C, was treated
with a solution of 2 equiv (excess) of [(Ph3P)Au]BF4, prepared
from 110 mg of Ph3AuCl and 43 mg of AgBF4 (0.22 mmol each)
in 10 mL of tetrahydrofuran at -78 °C. The mixture was
warmed to 20 °C with stirring within 2 h, and the solvent was
evaporated. The residue was extracted with dichloromethane
and the product precipitated from the extract by addition of
diethyl ether. The yellow solid was collected and recrystallized
from acetone/n-pentane: 84 mg (51% yield); mp 194 °C (dec).
NMR spectra were obtained in CD2Cl2 at 25 °C. 31P NMR: 37.1
(s, 2P); 29.7 (s, 1P). 13C NMR: 134.64-129.35 (Ph); C-CN and
C(CN) not detected. 1H NMR: 8.3-7.15 (m, Ph). MS (FAB):
m/z 1556 (11.63) [M - BF4]+, 721 (91.34) [L2Au]+, 459 (100)
[LAu]+. IR: 2161.5 cm-1. Anal. Calcd for C62H50Au3NO2P3SBF4
(1643.71): C, 45.30; H, 3.06. Found: C, 46.25; H, 3.15.
Deter m in a tion of th e Cr ysta l Str u ctu r es. Specimens of
suitable quality and size of [(Ph3P)Au]2C(SO2Me)2, [(Ph3As)-
Au]2C(SO2Me)2, [(MePh2P)Au]2C(SO2Me)2, [(Ph3P)Au]2C(SO2-
Ph)2,{[(Ph3P)Au]2C(SO2Ph)CN[Au(PPh3)]}+BF4-, [(Ph3P)Au]2-
C(SO2Ph)CN, [(Ph3P)Au]CHPh(SO2Ph), and [(Ph3P)Au]2C-
(d ) R ) Me, L ) P h 2MeP : 43.0 mg (0.25 mmol) of sulfone,
216 mg (0.5 mmol) of LAuCl, 2 × 20 mL of solvent. Yield: 221
mg (92%). Mp: 194 °C dec. Single crystals were grown from
dichloromethane/n-pentane on cooling to -10 °C. NMR spectra
were obtained in CD2Cl2 at 25 °C. 31P NMR: 22.8 (s). 13C
1
NMR: 14.42 (d, J (PC) ) 38, PMe); 48.82 (s, SMe); 133.08 (d,
J ) 14.0), 132.18 (s), 130.82 (d, J ) 54.5), and 129.62 (d, J )
1
3
12.0) for o-, p-, i-, and m-C of Ph. H NMR: 2.21 (d, J (PH) )
17, PMe, 6H); 3.19 (s, SMe, 6H); 7.69-7.37 (m, Ph, 20H). MS
(FAB): m/z 964 (3.95) [M]+, 595 (42.57) [L2Au]+, 396 (100)
[LAu]+. Anal. Calcd for C29H32Au2P2O4S2‚0.5C5H12 (1000.65):
C, 37.97; H, 3.87. Found: C, 37.62; H, 3.76.
(e) R ) P h , L ) P h 3P : 75 mg (0.25 mmol) of sulfone, 250
mg (0.5 mmol) of LAuCl, 2 × 20 mL of solvent. Yield: 267 mg
(88%). Mp: 195 °C dec. Single crystals were grown from