Koshevoy et al.
The reaction mixture was stirred for 30 min. The yellow transparent
solution was diluted with toluene (5 cm3), concentrated to a volume
of ca. 7 cm3. The yellow solid was separated by centrifugation,
washed with toluene (5 cm3) and diethyl ether (3 × 5 cm3), and
vaccuum-dried (236 mg, 95%). An analytically pure sample was
obtained by recrystallization from CH2Cl2/diethyl ether at +5 °C.
31P{1H} NMR (CDCl3; δ): 42.0 (s). 1H NMR (CDCl3; δ): 7.63-7.46
(m, 24H), 7.41 (dm, C6H4-N(CH3)2, J(H-H) 9.0 Hz, 4H), 6.61
(dm, C6H4-N(CH3)2, J(H-H) 9.0 Hz, 4H), 2.96 (s, N(CH3)2, 12H).
Anal. calcd for C50H44Au2N2P2: C, 53.20; H, 3.93; N, 2.48. Found:
C, 53.01; H, 3.95; N, 2.40.
or diethyl ether into their acetone solutions at +5 °C. Complex
[{Au3Cu2(C2Ph)6}Au3(PPh2C6H4PPh2)3][PF6]2 (9) was reported
earlier.6
[{Au3Cu2(C2C6H4NO2)6}Au3(PPh2C6H4PPh2)3][PF6]2 (8). An
orange compound was formed. Yield: 82%. ES MS (m/z):
[Au6Cu2(C2C6H4NO2)6(PPh2C6H4PPh2)3]2+, 1762 (calcd, 1762).
31P{1H} NMR (acetone-d6; δ): 44.7 (s, 3P), -144.8 (sept, 1P, PF6).
1H NMR (acetone-d6; δ), {Au(C2C6H4NO2)2}: 7.65 (d, H-meta,
12H, J(H-H) 8.8 Hz), 7.11 (dd, H-ortho, 12H, J(H-H) 8.8 Hz).
1H NMR (acetone-d6; δ), diphosphine: 8.02 (dm(AXX′), H-ortho,
24H, J(H-H) 6.7, J(P-H) 13.6 Hz), 7.91 (m(A2X2), {P-C6H4-P}
12H, <J(P-H)> 3.4 Hz), 7.68 (t, H-para, 12H, J(H-H) 7.5 Hz),
7.51 (dd, H-meta, 24H, J(H-H) 6.7, 7.5 Hz). 13C NMR (acetone-
d6; δ), {Au(C2C6H4NO2)2}: 148.33 (s, C-para-NO2), 134.47 and
124.78 (s, C-meta and C-ortho), 123.52 (s, C-ipso), 112.86 (s,
Ct C-Au), 117.39 (s, Ct C-Au). 13C NMR (acetone-d6; δ),
diphosphine: 137.12 (m (AXX′), C (-C6H4-), J(P-C) 59 Hz),
136.92 (m (AXX′), C-ortho, J(P-C) 16.5 Hz), 135.73 (m (AXX′),
C(H) (-C6H4-), J(P-C) ca. 12 Hz), 134.63 (s, C-para), 131.61
(m (AXX′), C-meta, J(P-C) 11.9 Hz), 129.50 (m (AXX′), C-ipso,
J(P-C) 56.7 Hz). Anal. calcd for C138H96Au6Cu2F12N6O12P8: C,
43.45; H, 2.54; N, 2.20. Found: C, 43.34; H, 2.87; N, 2.16.
[{Au3Cu2(C2C6H4OMe)6}Au3(PPh2C6H4PPh2)3][PF6]2 (10). An
orange-red compound was formed. Yield: 86%. ES MS (m/z):
[Au6Cu2(C2C6H4OMe)6(PPh2C6H4PPh2)3]2+, 1717 (calcd, 1717).
31P{1H} NMR (acetone-d6; δ): 43.4 (s, 3P), -144.8 (sept, 1P, PF6).
1H NMR (acetone-d6; δ), {Au(C2C6H4NO2)2}: 6.69 (d, H-ortho,
12H, J(H-H) 8.7 Hz), 6.39 (dd, H-meta, 12H, J(H-H) 8.7 Hz),
(AuC2C6H4NO2)2P(NC4H4)2C6H4P(NC4H4)2 (5). Complex 5
was generated analogously to 3, using (AuC2C6H4NO2)n (150 mg,
0.437 mmol) and 1,4-bis(dipyrrolylphosphino)benzene (92 mg,
0.229 mmol). Yield: 202 mg, 85%. An analytically pure sample
was obtained by recrystallization from CH2Cl2/diethyl ether at +5
1
°C. 31P{1H} NMR (CDCl3; δ): 95.0 (s, br). H NMR (CDCl3; δ):
8.15 (dm, C6H4-NO2, J(H-H) 8.9 Hz, 4H), 7.59 (dm, C6H4-NO2,
J(H-H) 8.9 Hz, 4H), 7.38 (m, P-C6H4-P, 4H), 7.10 (m, NC4H4,
8H), 6.52 (dm, NC4H4, J(H-H) 1.8 Hz, 8H). Anal. calcd for
C38H28Au2N6O4P2: C, 41.93; H, 2.59; N, 7.72. Found: C, 42.23; H,
2.59; N, 7.39.
(AuC2Ph)2P(NC4H4)2C6H4P(NC4H4)2 (6). (AuC2C6H5)n (150
mg, 0.503 mmol) was suspended in CH2Cl2 (10 cm3), and 1,4-
bis(dipyrrolylphosphino)benzene (106 mg, 0.264 mmol) was added.
The reaction mixture was stirred for 30 min. The resulting
suspension was evaporated, dissolved in CHCl3 (ca. 35 cm3), diluted
with toluene (5 cm3), and treated as 2. A pale yellowish solid was
formed, 230 mg, 92%. An analytically pure sample was obtained
by recrystallization from CH2Cl2/diethyl ether at +5 °C. 31P{1H}
NMR (CDCl3; δ): 95.5 (s, br). 1H NMR (CDCl3; δ): 7.50 (m, 4H),
7.37-7.23 (m, 10H), 7.11 (m, NC4H4, 8H), 6.50 (dm, NC4H4,
J(H-H) 2.1 Hz, 8H). Anal. calcd for C38H30Au2N4P2: C, 45.71; H,
3.03; N, 5.61. Found: C, 45.94; H, 3.08; N, 5.50.
(AuC2C6H4OMe)2P(NC4H4)2C6H4P(NC4H4)2 (7). (AuC2C6H4-
OMe)n (150 mg, 0.457 mmol) was suspended in CH2Cl2 (10 cm3),
and 1,4-bis(dipyrrolylphosphino)benzene (95 mg, 0.236 mmol) was
added. The reaction mixture was stirred for 30 min. The white
suspension was diluted with toluene (10 cm3), and the solid was
separated by centrifugation, washed with toluene (5 cm3) and diethyl
ether, and dried under a vacuum. The product (220 mg, 91%) was
obtained as a white powder. An analytically pure sample was
obtained by extraction with chloroform passing through a layer of
neutral Al2O3 (1 × 4 cm), evaporation, and washing of the residue
with diethyl ether. 31P{1H} NMR (CDCl3; δ): 95.7 (s, br). 1H NMR
(CDCl3; δ): 7.45 (dm, C6H4-OCH3, J(H-H) 8.8 Hz, 4H), 7.32
(m, P-C6H4-P, 4H), 7.10 (m, NC4H4, 8H), 6.83 (dm, C6H4-OCH3,
J(H-H) 8.8 Hz, 4H), 6.49 (m, NC4H4, 8H), 3.81 (s, OCH3, 6H).
Anal. calcd for C40H34Au2N4O2P2: C, 45.38; H, 3.24; N, 5.29.
Found: C, 45.53; H, 3.26; N, 5.24.
1
3.72 (s, 18H, OMe). H NMR (acetone-d6; δ), diphosphine: 7.97
(dm(AXX′), H-ortho, 24H, J(H-H) 6.7, J(P-H) 7.3 Hz), 7.75
(m(A2X2), {P-C6H4-P} 12H, <J(P-H)> 3.4 Hz), 7.66 (t, H-para,
12H, J(H-H) 7.5 Hz), 7.48 (dd, H-meta, 24H, J(H-H) 6.7, 7.5
Hz). 13C NMR (acetone-d6; δ), {Au(C2C6H4NO2)2}: 161.24 (s,
C-para-OMe), 135.07 and 115.07 (s, C-meta and C-ortho), 117.67
(s, C-ipso), 114.43 (s, Ct C-Au), 110.94 (s, Ct C-Au), 56.35 (s,
OMe). 13C NMR (acetone-d6; δ), diphosphine: 137.43 (m (AXX′),
C (-C6H4-), J(P-C) 59 Hz), 137.03 (m (AXX′), C-ortho, J(P-C)
16.4 Hz), 135.61 (m (AXX′), C(H) (-C6H4-), J(P-C) ca. 11 Hz),
134.55 (s, C-para), 131.61 (m (AXX′), C-meta, J(P-C) 11.8 Hz),
130.01 (m (AXX′), C-ipso, J(P-C) 55.2 Hz). Anal. calcd for
C
144H114Au6Cu2F12O6P8: C, 46.43; H, 3.08. Found: C, 46.51; H,
3.15.
[{Au3Cu2(C2C6H4NMe2)6}Au3(PPh2C6H4PPh2)3][PF6]2 (11). A
very dark red compound was formed. Yield: 71%. ES MS (m/z):
[Au6Cu2(C2C6H4NMe2)6(PPh2C6H4PPh2)3]2+, 1756 (calcd, 1756).
31P{1H} NMR (acetone-d6; δ): 42.9 (s, 3P), -144.8 (sept, 1P, PF6).
1H NMR (acetone-d6; δ), {Au(C2C6H4NMe2)2}: 6.58 (d, H-ortho,
12H, J(H-H) 8.8 Hz), 6.39 (dd, H-meta, 12H, J(H-H) 8.8 Hz),
1
2.90 (s, 36H, NMe2). H NMR (acetone-d6; δ), diphosphine: 7.98
(dm(AXX′), H-ortho, 24H, J(H-H) 6.7, J(P-H) 6.7 Hz), 7.73
(m(A2X2), {P-C6H4-P} 12H, <J(P-H)> 3.3 Hz), 7.64 (t, H-para,
12H, J(H-H) 7.5 Hz), 7.45 (dd, H-meta, 24H, J(H-H) 6.7, 7.5
Hz). 13C NMR (acetone-d6; δ), {Au(C2C6H4NMe2)2}: 151.50 (s,
C-para-NMe2), 135.10 and 113.29 (s, C-meta and C-ortho), 112.91
(s, C-ipso), 115.70 (s, Ct C-Au), 109.87 (s, Ct C-Au), 41.24 (s,
NMe2). 13C NMR (acetone-d6; δ), diphosphine: 137.50 (m (AXX′),
C (-C6H4-), J(P-C) 59 Hz), 136.99 (m (AXX′), C-ortho, J(P-C)
16.4 Hz), 135.51 (m (AXX′), C(H) (-C6H4-), J(P-C) ca. 11 Hz),
134.36 (s, C-para), 131.62 (m (AXX′), C-meta, J(P-C) 11.7 Hz),
130.21 (m (AXX′), C-ipso, J(P-C) 54.5 Hz). Anal. calcd for
General Procedure for the Preparation of Heterometallic
Au-Cu Complexes. Complexes 2-7 (0.100 mmol) were sus-
pended in CH2Cl2 (8 cm3) and diluted with diethyl ether (4 cm3),
and a solution of Cu(NCMe)4PF6 (0.067 mmol) in CH2Cl2 (3
cm3) was added dropwise to afford a transparent orange to red
solution (except 12, orange suspension formed). The solvent was
removed on a rotovap (12 was separated from the pale solution
by centrifugation). The solid residue was dissolved in acetone
(3 cm3), filtered, and precipitated by the addition of hexane or
diethyl ether to give a microcrystalline solid. If necessary, the
samples were recrystallized by the gas-phase diffusion of pentane
C150H132Au6Cu2F12N6P8: C, 47.37; H, 3.50; N, 2.21. Found: C,
47.53; H, 3.46; N, 2.13.
2096 Inorganic Chemistry, Vol. 48, No. 5, 2009