4380 Organometallics, Vol. 23, No. 19, 2004
Blanco et al.
PPhH-). 19F NMR (CDCl3, RT), δ: -120.4 (m, 8F, Fo), -158.8
led to the precipitation of 9 as a white solid. Yield: 0.13 g
(62%). 31P{1H} NMR (CDCl3, RT), δ: 45.0 [d, 1P, 2J (P-P) )
254 Hz, PPh3), 7.0 (t, 1P, PPh2-). 19F NMR (CDCl3, RT), δ:
-114.9 (m, 2F, Fo), -161.4 [t, 1F, 3J (Fm-Fp) ) 19.8 Hz, Fp],
3
[t, 4F, J (Fm-Fp) ) 19.9 Hz, Fp], -162.3 (m, 8F, Fm), -120.9
3
(m, 4F, Fo), -159.1 [t, 2F, J (Fm-Fp) ) 20.1 Hz, Fp], -162.4
(m, 4F, Fm). 1H NMR (CDCl3, RT), δ: 7.63-6.79 (m, 35H, Ph),
5.32 (d, 1H, PPhH-). Anal. Calcd for C78H36Au2F30P3N
(2043.91): C, 45.85; H, 1.75; N, 0.7. Found: C, 45.85; H, 2.05;
N, 0.75. ΛM: 82 Ω-1 cm2 mol-1. ES(-) m/z (%): 1505 [M]- (100).
Syn th esis of P P N[{Au (C6F 5)3(µ-P P h H)}2Au ] (6). PPN-
[Au(acac)2]42 (0.1 mmol, 0.093 g) was added to a solution of
compound 2 (0.2 mmol, 0.161 g) in dichloromethane (20 mL).
After 1 h of stirring the solvent was evaporated, and addition
of hexane led to the precipitation of 6 as a white solid. Yield:
0.14 g (58%). (NMR signals corresponding to two different
diastereoisomeric pairs.) 31P{1H} NMR (CDCl3, RT), δ: 21.1
(s, 2P, PPN), -31.0 (s, 2P, PPhH-), -33.3 (s, 2P, PPhH-). 19F
NMR (CDCl3, RT), δ: -119.7 (m, 4F, Fo), -159.3 [t, 2F, 3J (Fm-
Fp) ) 19.2 Hz, Fp], -162.5 (m, 4F, Fm), -120.6 (m, 2F, Fo),
3
-163.3 (m, 2F, Fm), -116.3 (m, 2F, Fo), -161.4 [t, 1F, J (Fm-
Fp) ) 20.4 Hz, Fp], -163.7 (m, 2F, Fm), -117.1 (m, 2F, Fo),
3
-162.7 [t, 1F, J (Fm-Fp) ) 20.4 Hz, Fp], -163.7 (m, 2F, Fm),
-118.8 (m, 2F, Fo), -162.7 [t, 1F, 3J (Fm-Fp) ) 20.4 Hz, Fp],
-164.5 (m, 2F, Fm). 1H NMR (CDCl3, RT), δ: 7.80-6.76 (m,
50H, Ph). Anal. Calcd for C84H50Au3F20P4N (2167.78): C, 46.55;
H, 1.85; N, 0.55. Found: C, 49.0; H, 1.9; N, 0.9. ΛM: 100 Ω-1
cm2 mol-1. ES(-) m/z (%): 1629 [M]- (95).
Syn th esis of P P N[{Au (C6F5)3}2(µ3-P P h ){Au (P P h 3)}] (10).
[Au(acac)(PPh3)] (0.1 mmol, 0.056 g) was added to a freshly
prepared solution of 5 (0.1 mmol, 0.204 g) in dichloromethane
(20 mL). After 1 h of stirring, the solvent was partially
evaporated and hexane was added to afford 10 as a white solid.
Yield: 0.05 g (20%). 31P{1H} NMR (CDCl3, RT), δ: 21.1 (s, 2P,
PPN), 42.6 (d, 1P, 2J (P-P) ) 269 Hz, PPh3], -8.7 (d, 1P,
PPh2-). 19F NMR (CDCl3, RT), δ: -116.6 (m, 4F, Fo), -160.8
3
-159.7 [t, 1F, J (Fm-Fp) ) 20.0 Hz, Fp], -162.5 (m, 2F, Fm);
-120.0 (m, 4F, Fo), -159.4 [t 2F, 3J (Fm-Fp) ) 19.2 Hz, Fp],
3
-162.5 (m, 4F, Fm), -120.6 (m, 2F, Fo), -159.7 [t, 1F, J (Fm-
1
3
Fp) ) 20.0 Hz, Fp], -162.5 (m, 2F, Fm). H NMR (CDCl3, RT),
[t, 2F, J (Fm-Fp) ) 20.2 Hz, Fp], -162.9 (m, 2F, Fm), -117.8
δ: 7.75-7.12 (m, 40H, Ph), 5.70 (d, 2H, PPhH-), 5.53 (d, 2H,
PPhH-). Anal. Calcd for C84H42Au3F30P4N (2350.06): C, 42.95;
H, 1.8; N, 0.6; Found: C, 42.8; H, 1.9; N, 0.6. ΛM: 94 Ω-1 cm2
mol-1. ES(-) m/z (%): 1811 [M]- (100).
(m, 4F, Fo), -161.1 [t, 1F, 3J (Fm-Fp) ) 20.3 Hz, Fp], -162.9
(m, 4F, Fm), -119.9 (m, 4F, Fo), -161.1 [t, 2F, 3J (Fm-Fp) )
20.3 Hz, Fp], -163.8 (m, 4F, Fm). 1H NMR (CDCl3, RT), δ:
7.63-6.65 (m, 50H, Ph). Anal. Calcd for C96H50Au3F30P4N
(2502.57): C, 46.1; H, 2.0; N, 0.55. Found: C, 45.7; H, 2.45;
Syn th esis of P P N[{Au (C6F 5)3(µ-P P h H)}2Ag] (7). A solu-
tion of Ag(OClO3) (0.1 mmol, 0.021 g) in diethyl ether (10 mL)
was added to a solution of compound 2 (0.2 mmol, 0.161 g)
and PPN(acac) (0.2 mmol, 0.127 g) in dichloromethane (10 mL).
After 1 h of stirring the solvent was evaporated, diethyl ether
(20 mL) was added, and the mixture was filtered to remove
the insoluble PPN(ClO4). Concentration of the solution and
addition of hexane (20 mL) led to the precipitation of 7 as a
white solid. Yield: 0.11 g (48%). (NMR signals corresponding
to two different diastereoisomeric pairs.) 31P{1H} NMR (CDCl3,
223 K), δ: 21.1 (s, 2P, PPN), -66.3 [s, 2P, J (P-109Ag) ) 514,
J (P-107Ag) ) 445 Hz, PPhH-]; -69.3 [s, 2P, J (P-109Ag) ) 511,
J (P-107Ag) ) 444 Hz, PPhH-]. 19F NMR (CDCl3, RT), δ: -119.7
(m, 4F, Fo), -158.8 [t, 2F, 3J (Fm-Fp) ) 20.3 Hz, Fp], -161.9
N, 0.5. ΛM: 108 Ω-1 cm2 mol-1
.
Syn t h esis of (P P N)2[{Au (C6F 5)3}2(µ3-P P h ){Au (C6F 5)}]
(11). To a freshly prepared solution of 5 (0.1 mmol, 0.204 g)
in dichloromethane (20 mL) were added [Au(C6F5)(tht)] (0.1
mmol, 0.045 g) and PPN(acac) (0.1 mmol, 0.064 g). After
stirring for 1 h partial evaporation of the solvent and addition
of hexane led to the precipitation of 11 as a white solid. Yield:
0.18 g (61%). 31P{1H} NMR (CDCl3, RT), δ: 21.1 (s, 4P, PPN),
-1.4 (s, 1P, PPh2-). 19F NMR (CDCl3, RT), δ: -115.2 (m, 2F,
Fo), -161.9 [t, 1F, 3J (Fm-Fp) ) 19.8 Hz, Fp], -164.5 (m, 2F,
3
Fm), -116.6 (m, 4F, Fo), -163.4 [t, 2F, J (Fm-Fp) ) 20.4 Hz,
Fp], -164.5 (m, 4F, Fm), -117.9 (m, 4F, Fo), -163.4 [t, 2F,
3J (Fm-Fp) ) 20.4 Hz, Fp], -164.5 (m, 4F, Fm), -118.8 (m, 4F,
Fo), -163.4 [t, 2F, 3J (Fm-Fp) ) 20.4 Hz, Fp], -164.5 (m, 4F,
3
(m, 4F, Fm), -120.8 (m, 2F, Fo), -159.2 [t, 1F, J (Fm-Fp) )
1
20.0 Hz, Fp], -161.9 (m, 2F, Fm); -120.2 (m, 4F, Fo), -159.0
Fm). H NMR (CDCl3, RT), δ: 7.64-7.33 (m, 65H, Ph). Anal.
3
[t, 2F, J (Fm-Fp) ) 20.3 Hz, Fp], -161.9 (m, 4F, Fm), -120.8
Calcd for C120H65Au3F35P5N2 (2945.62): C, 48.95; H, 2.2; N,
3
0.95. Found: C, 48.95; H, 2.0; N, 0.8. ΛM: 191 Ω-1 cm2 mol-1
.
(m, 2F, Fo), -159.3 [t, 1F, J (Fm-Fp) ) 20.0 Hz, Fp], -161.9
(m, 2F, Fm). 1H NMR (CDCl3, RT), δ: 7.69-7.12 (m, 40H, Ph),
4.80 (d, 2H, PPhH-); 4.66 (d, 2H, PPhH-). Anal. Calcd for
ES(-) m/z (%): 934 [M]2- (25).
Syn th esis of (P P N)3[{(Au (C6F 5)3)2(µ3-P P h )2}2Au ] (12).
To a freshly prepared solution of 5 (0.2 mmol, 0.409 g) in
dichloromethane (20 mL) was added PPN[Au(acac)2] (0.1
mmol, 0.093 g). After stirring for 1 h, partial evaporation of
the solvent and addition of hexane led to the precipitation of
12 as a white solid. Yield: 0.37 g (76%). 31P{1H} NMR (CDCl3,
RT), δ: 21.1 (s, 6P, PPN), 12.8 (s, 2P, PPh2-). 19F NMR (CDCl3,
RT), δ: -116.8 (m, 4F, Fo), -158.8 [t, 2F, 3J (Fm-Fp) ) 19.9
Hz, Fp], -162.1 (m, 4F, Fm), -117.4 (m, 4F, Fo), -158.8 [t 2F,
3J (Fm-Fp ) 19.9 Hz, Fp], -162.4 (m, 4F, Fm), -118.9 (m, 4F,
Fo), -158.8 [t, 2F, 3J (Fm-Fp) ) 19.9 Hz, Fp], -162.4 (m, 4F,
C
84H42AgAu2F30P4N (2260.87): C, 44.65; H, 1.85; N, 0.6.
Found: C, 45.05; H, 2.0; N, 0.6. ΛM: 97 Ω-1 cm2 mol-1. ES(-)
m/z (%): 1723 [M]- (100).
Syn th esis of [Au (C6F5)3(µ3-P P h ){Au (P P h 3)}2] (8). Meth od
1. [Au(acac)(PPh3)] (0.2 mmol, 0.112 g) was added to a freshly
prepared solution of 2 (0.1 mmol, 0.081 g) in dichloromethane
(20 mL). After 1 h stirring, the solvent was partially evapo-
rated and hexane was added to afford 8 as a white solid.
Yield: 0.13 g (74%).
Meth od 2. [Au(acac)(PPh3)] (0.1 mmol, 0.056 g) was added
to a solution of compound 3 (0.1 mmol, 0.127 g) in dichlo-
romethane (20 mL). After 1 h of stirring the solvent was
evaporated, and addition of hexane led to the precipitation of
8 as a white solid. Yield: 0.12 g (68%). 31P{1H} NMR (CDCl3,
RT), δ: 45.1 [d, 2P, 2J (P-P) ) 268 Hz, PPh3), 1.1 (t, 1P, PPh2-).
19F NMR (CDCl3, RT), δ: -117.5 (m, 4F, Fo), -160.5 [t, 2F,
3J (Fm-Fp) ) 20.0 Hz, Fp], -162.7 (m, 4F, Fm), -120.7 (m, 2F,
3
Fm), -120.0 (m, 8F, Fo), -162.6 [t, 4F, J (Fm-Fp) ) 20.3 Hz,
Fp], -164.3 (m, 8F, Fm), -120.3 (m, 4F, Fo), -161.7 [t, 2F,
3J (Fm-Fp) ) 20.3 Hz, Fp], -163.4 (m, 4F, Fm). 1H NMR (CDCl3,
RT), δ: 7.68-6.57 (m, 100H, Ph). Anal. Calcd for C192H100
Au5F60P8N3 4821.36): C, 47.85; H, 2.1; N, 0.9. Found: C, 47.4;
H, 2.45; N, 0.9. ΛM: 284 Ω-1 cm2 mol-1
-
.
Syn th esis of [Au (C6F 5)2(µ-P P h H)]3 (13). PPhH2 (0.4
mmol, 0.045 mL) was added to a solution of [Au(C6F5)2(µ-Cl)2]43
(0.2 mmol, 0.227 g) in diethyl ether (20 mL), leading to a yellow
solution. After stirring for 90 min, the solvent was partially
3
Fo), -160.3 [t, 1F, J (Fm-Fp) ) 20.1 Hz, Fp], -162.6 (m, 2F,
1
Fm). H NMR (CDCl3, RT), δ: 7.55-6.92 (m, 35H, Ph). Anal.
Calcd for C60H35Au3F15P3 (1724.72): C, 41.75; H, 2.05. Found:
C, 41.85; H, 2.5. ΛM: 12 Ω-1 cm2 mol-1
.
evaporated and hexane was added to afford 13 as
a
Syn t h esis of P P N[Au (C6F 5)3(µ3-P P h ){Au (C6F 5)}{Au -
(P P h 3)}] (9). To a solution of compound 3 (0.1 mmol, 0.127 g)
in dichloromethane (20 mL) were added [Au(C6F5)(tht)] (0.1
mmol, 0.045 g) and PPN(acac) (0.1 mmol, 0.064 g). After 1 h
of stirring the solvent was evaporated and addition of hexane
(43) Uso´n, R.; Laguna, A.; Laguna, M.; Abad, M. J . Organomet.
Chem. 1983, 249, 437.
(44) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.