C48H42Cl2IP3PdRu: C, 51.66; H, 3.70. Found: C, 51.36; H,
3.52%.
28 Hz). HRMS (FAB): calc. for C48H42P3BrClRuAu
m/z 1089.0392 (M Ϫ Cl)ϩ, found 1089.0398. Anal. Calc. for
C48H42P3BrClRuAu: C, 51.24; H, 3.76. Found: C, 51.49; H,
3.67%.
Cp(PPh3)Ru(ꢁ-Cl)(ꢁ-dppm)Pd(CH3)Cl (5). In a 25 ml Schlenk
flask, CpRu(PPh3)(η1-dppm)Me (0.200 g, 0.242 mmol) and
Pd(COD)Cl2 (0.069 g, 0.24 mmol) were dissolved in 10 ml of
benzene. The clear solution was stirred at room temperature for
4 h, during which a precipitate formed. The solid was filtered
with a frit, washed with pentane, and dried under vacuum.
Yield: 0.224 g (92%). Single crystals suitable for X-ray diffrac-
tion were grown by slow diffusion of pentane into a solution of
the orange product 5 in 1,2-dichloroethane. 1H NMR (CDCl3):
δ 8.06–5.90 (m, 35H, Ph2PCH2PPh2 ϩ PPh3), 4.58 (s, 5H, Cp),
Cp(PPh3)RuCl[ꢁ-PPh2(CH2)4PPh2]AuCl (10). The reaction
was performed similarly as for 8 starting from CpRu(PPh3)-
(η1-dppb)Cl (0.200 g, 0.224 mmol) and AuCl (0.052 g,
0.224 mmol). Yield: 0.202 g (94%). Single crystals suitable for
X-ray diffraction were grown by slow diffusion of pentane into
1
a solution of the yellow product 10 in dichloromethane. H
NMR (CDCl3): δ 7.84–7.00 (m, 35H, Ph2P(CH2)4PPh2 ϩ PPh3),
4.11 (s, 5H, Cp), 2.12 (m, 3H, dppb), 1.18 (m, 3H, dppb), 0.58
2.86 (m, 2H, Ph2PCH2PPh2), 0.39 (d, 3H, CH3, JPH = 3 Hz). 31
P
(m, 2H, dppb). 31P NMR (CDCl3): δ 44.8 (d, PPh3–Ru, JPP
=
NMR (CDCl3): δ 45.6 (dd, Ru–Ph2PCH2PPh2, JPP = 36, 27 Hz),
39.3 (d, Ru–PPh3, JPP = 36 Hz), 25.5 (d, Ph2PCH2PPh2–Pd,
JPP = 27 Hz). HRMS (FAB): calc. for C49H45P3ClRuPd
m/z 969.0501 (M Ϫ Cl)ϩ, found 969.0494. Anal. Calc. for C49-
H45Cl2P3PdRu: C, 58.57; H, 4.42. Found: C, 57.86; H, 3.94%.
42 Hz), 37.0 (d, Ru–Ph2P(CH2)4PPh2, JPP = 42 Hz), 31.6 (s,
Ph2P(CH2)4PPh2–Au). HRMS (FAB): calc. for C51H48P3Cl2-
RuAu m/z 1122.1055 (Mϩ), found 1122.1055. Anal. Calc. for
C51H48P3Cl2RuAu: C, 54.56; H, 4.31. Found: C, 54.30; H,
4.02%.
Cp(PPh3)Ru(ꢁ-I)(ꢁ-dppm)PtCl2 (6). The reaction was per-
formed similarly as for 4 starting from CpRu(PPh3)(η1-dppm)I
(0.200 g, 0.213 mmol) and Pt(COD)Cl2 (0.080 g, 0.21 mmol).
Cp(PPh3)RuCl(ꢁ-Ph2PNHPPh2)AuCl (11). The reaction was
performed similarly as for 8 starting from CpRu(PPh3)(η1-
Ph2PNHPPh2)Cl (0.200 g, 0.235 mmol) and AuCl (0.0546 g,
0.235 mmol). Yield: 0.208 g (81.6%). 1H NMR (CDCl3): δ 7.93–
6.91 (m, 35H, Ph2PCH2PPh2 ϩ PPh3), 5.93 (m, 1H, Ph2P-
NHPPh2), 4.12 (s, 5H, Cp). 31P NMR (CDCl3): δ 87.7 (dd, Ru–
Ph2PNHPPh2, JPP = 46, 38 Hz), 54.0 (d, PPh3–Ru, JPP = 38 Hz),
40.4 (d, Ph2PNHPPh2–Au, JPP = 46 Hz). HRMS (FAB): calc.
for C47H41NCl2P3RuAu m/z 1046.0850 (M Ϫ Cl)ϩ, found
1046.0876. Anal. Calc. for C48H42P3I2RuAu: C, 52.19; H, 3.82;
N, 1.29. Found: C, 51.71; H, 3.52; N, 1.21%.
1
Yield: 0.188 g (73%). H NMR (CDCl3): δ 8.04–6.12 (m, 35H,
Ph2PCH2PPh2 ϩ PPh3), 4.63 (s, 5H, Cp), 3.45 (m, 1H, Ph2P-
CHHPPh2), 2.94 (m, 1H, Ph2PCHHPPh2). 31P NMR (CDCl3):
δ 46.4 (dd, Ru–Ph2PCH2PPh2, JPP = 11, 35 Hz), 40.5 (d, Ru–
PPh3, JPP = 3, 35 Hz), Ϫ7.7 (d, Ph2PCH2PPh2–Pt, JPP = 3, 11
Hz). HRMS (FAB): calc. for C48H42IClP3PtRu m/z 1169.9924
(M Ϫ Cl)ϩ, found 1169.9916. Anal. Calc. for C48H42Cl2IP3PtRu:
C, 47.82; H, 3.51. Found: C, 47.60; H, 3.36%.
Cp(PPh3)Ru(ꢁ-I)(ꢁ-dppm)PtI2 (7). The reaction was per-
formed similarly as for 4 starting from CpRu(PPh3)(η1-dppm)I
(0.200 g, 0.213 mmol) and Pt(COD)I2 (0.119 g, 0.213 mmol).
Cp(PPh3)Ru(ꢁ-I)(ꢁ-dppm)CuI (12). In a 25 ml flask, CpRu-
(PPh3)(η1-dppm)I (0.200 g, 0.213 mmol) and CuI (0.203 g,
1.07 mmol) were dissolved in 10 ml of CH2Cl2. The red cloudy
mixture was stirred at room temperature overnight. After
the solids settled, the clear red supernatant was transferred to
another 25 ml Schlenk flask under N2 by means of a filter
cannula. The filtrate was condensed under vacuum to a small
volume (∼2 ml), and pentane (15 ml) was added through a
syringe to precipitate a red solid. The solid was filtered with a
medium swivel frit, washed with pentane (10 ml × 3), and dried
under vacuum. Yield: 0.216 g (90%). Single crystals suitable for
X-ray diffraction were grown by slow diffusion of pentane into
a solution of the red product 12 in dichloromethane. 1H NMR
(CDCl3): δ 7.63–6.92 (m, 35H, Ph2PCH2PPh2 ϩ PPh3), 4.34
(s, 5H, Cp), 2.89 (m, 1H, Ph2PCHHPPh2), 2.51 (m, 1H, Ph2P-
CHHPPh2) 31P NMR (CDCl3): δ 40.3 (d, Ru–PPh3 JPP = 40 Hz),
26.7 (dd, Ru–Ph2PCH2PPh2, JPP = 40, 20 Hz), Ϫ18.5 (br s,
Ph2PCH2PPh2–Cu). HRMS (FAB): calc. for C48H42P3I2RuCu
m/z 1129.8928 (Mϩ) found 1129.8922. Anal. Calc. for
C48H42P3I2RuCu: C, 51.01; H, 3.75. Found: C, 51.25; H, 3.54%.
1
Yield: 0.266 g (90%). H NMR (CDCl3): δ 8.12–5.76 (m, 35H,
Ph2PCH2PPh2 ϩ PPh3), 4.65 (s, 5H, Cp), 3.52 (m, 1H, Ph2-
PCHHPPh2), 3.12 (m, 1H, Ph2PCHHPPh2). 31P NMR (CDCl3):
δ 45.8 (dd, Ru–Ph2PCH2PPh2, JPP = 12 Hz, 35 Hz), 40.4 (dd,
Ru–PPh3, JPP = 3, 35 Hz), Ϫ2.1 (dd, Ph2PCH2PPh2–Pt, JPP = 3,
12 Hz). HRMS (FAB): calc. for C48H42I3P3PtRu m/z 1261.9280
(M Ϫ I)ϩ, found 1261.9274. Anal. Calc. for C48H42I3P3PtRu:
C, 41.52; H, 3.05. Found: C, 41.24; H, 2.79%.
Cp(PPh3)RuI(ꢁ-dppm)AuI (8). In a 20 ml Schlenk flask,
CpRu(PPh3)(η1-dppm)I (0.200 g, 0.213 mmol) and AuI
(0.069 g, 0.213 mmol) were slurried in 10 ml of CH2Cl2. The
mixture was stirred at room temperature for 5 h, during which
the solid AuI dissolved to afford a clear orange–red solution.
The solution was condensed under vacuum to a small volume
(∼3 ml), and hexane (15 ml) was transferred through a syringe
to precipitate a red solid. The solid was filtered with a medium
swivel frit, washed with hexanes, and dried under vacuum.
1
Yield: 0.260 g (97%). H NMR (CDCl3): δ 8.07–6.13 (m, 35H,
X-Ray crystallography
Ph2PCH2PPh2 ϩ PPh3), 5.04 (m, 1H, Ph2PCHHPPh2), 4.16
(s, 5H, Cp), 1.60 (m, 1H, Ph2PCHHPPh2). 31P NMR (CDCl3):
δ 41.7 (d, Ru–PPh3, JPP = 42 Hz), 31.4 (dd, Ru–Ph2PCH2PPh2,
JPP = 42, 25 Hz), 27.9 (d, Ph2PCH2PPh2–Au, JPP = 25 Hz).
HRMS (FAB): calc. for C48H42P3I2RuAu m/z 1137.0255 (M Ϫ
I)ϩ, found 1137.0246. Anal. Calc. for C48H42P3I2RuAu: C,
45.63; H, 3.35. Found: C, 45.70; H, 3.36%.
Crystallographic structure determination of complexes 4, 5, 10
and 12. Data for all four complexes were collected at 173 K on a
Siemens SMART PLATFORM equipped with a CCD area
detector and a graphite monochromator utilizing Mo-Kα
radiation (λ = 0.71073 Å). Cell parameters for each structure
were refined using up to 8192 reflections. A full sphere of
data (1850 frames) was collected using the ω-scan method
(0.3Њ frame width). The first 50 frames were remeasured at
the end of data collection to monitor instrument and crystal
stability (maximum correction on I was <1%). Absorption
corrections by integration were applied based on measured
indexed crystal faces. The structures were solved by direct
methods in SHELXTL,39 and refined using full-matrix least
squares. The non-H atoms were treated anisotropically, whereas
the hydrogen atoms were calculated in ideal positions and were
Cp(PPh3)RuBr(ꢁ-dppm)AuCl (9). The reaction was per-
formed similarly as for 311 starting from CpRu(PPh3)(η1-dpp-
m)Br (0.200 g, 0.224 mmol) and Au(PPh3)Cl (0.111 g, 0.224
1
mmol). Yield: 0.179 g (71.0%). H NMR (CDCl3): δ 7.96–6.86
(m, 35H, Ph2PCH2PPh2 ϩ PPh3), 4.86 (m, 1H, Ph2PCHHPPh2),
4.12 (s, 5H, Cp), 1.43 (m, 1H, Ph2PCHHPPh2). 31P NMR
(CDCl3): δ 42.5 (d, PPh3–Ru, JPP = 42 Hz), 34.2 (dd, Ru–Ph2P-
CH2PPh2, JPP = 42, 28 Hz), 22.0 (d, Ph2PCH2PPh2–Au, JPP
=
D a l t o n T r a n s . , 2 0 0 3 , 4 2 8 8 – 4 2 9 6
4295