Heterobimetallic MRh (M ) Pt, Pd) Complexes
Organometallics, Vol. 21, No. 13, 2002 2611
[(P P h 3)2P t(µ-BDT)Rh (CO)(P P h 3)]ClO4 (3c): yellow solid
(83% yield). H NMR (300 Hz, CDCl3, 20 °C): δ 2.40 (m, 1 H,
-CH2-, EDT), 6.8-7.4 (m, 60 H, Ph, PPh3, and P(OPh)3). Anal.
Calcd for PtRhClS2P4O10C74H64‚1/2CH2Cl2: C, 53.34; H, 3.87;
S, 3.81. Found: C, 53.09; H, 3.87; S, 3.77. FAB: m/z 1535 [MH
- ClO4]+, 914 [M - 2P(OPh)3 - ClO4]+.
Cr ysta l Da ta for Com p lexes [(P P h 3)2P t(µ-EDT)Rh -
(CO)2]BF 4 (2a ′) a n d 3a . Suitable crystals of complexes 2a ′
and 3a were grown by diffusing n-hexane into a solution of
the complex in dichloromethane and mounted on a glass fiber.
The data were collected and processed at room temperature
on a Mar Research image plate scanner. Graphite-monochro-
mated Mo KR radiation was used to measure 95/2 frames, 180
s per frame in both cases.
1
-SCH2-, BDT), 2.18 (m, 3 H, -SCH2-, BDT), 1.98 (m, 2 H,
-CH2-, BDT), 1.38 (m, 1 H, -CH2-, BDT), 1.17 (m, 1 H,
-CH2-, BDT), 7.1-7.6 (m, 45 H, Ph, PPh3). IR (KBr, cm-1):
ν(CO), 1979 (vs). Anal. Calcd for PtRhClS2P3O5C59H53
: C,
51.52; H, 3.93; S, 4.65. Found: C, 51.39; H, 3.87; S, 4.64.
FAB: m/z 1233 [MH - ClO4]+.
[(d p p p )P t (µ-E DT)R h (CO)(P P h 3)]ClO4‚1/2CH 2Cl2 (3d ):
yellow solid (72% yield). 1H NMR (300 MHz, CDCl3, 20 °C): δ
3.00 (m, 1 H, -SCH2-, EDT), 2.85 (m, 1 H, -SCH2-, EDT),
2.38 (m, 1 H, -SCH2-, EDT), 2.15 (m, 1 H, -SCH2-, EDT),
6.8-7.8 (m, 35 H, Ph, dppp, PPh3), 2.7-2.8 (m, 4 H, -PCH2-,
dppp), 2.10 (m, 2 H, -CH2-, dppp). IR (KBr, cm-1): ν(CO),
1980 (vs). Anal. Calcd for PtRhClS2P3O5C48H45‚1/2CH2Cl2: C,
47.16; H, 3.72; S, 5.18. Found: C, 46.98; H, 3.69; S, 5.16.
FAB: m/z 1092 [M - ClO4]+.
[(d p p p )P t (µ-BDT)R h (CO)(P P h 3)]ClO4‚1/2CH 2Cl2 (3e):
yellow solid (84% yield). 1H NMR (300 MHz, CDCl3, 20 °C): δ
2.6-3.2 (a, 4 H, -SCH2-, BDT), 1.80 (m, 2 H, -CH2-, BDT),
1.65 (m, 2 H, -CH2-, BDT), 7.2-8.1 (m, 35 H, Ph, dppp, PPh3),
2.45 (m, 4 H, -PCH2-, dppp), 2.00 (m, 2 H, -CH2-, dppp).
IR (KBr, cm-1): ν(CO), 1988 (vs). Anal. Calcd for
PtRhClS2P3O5C50H49‚1/2CH2Cl2: C, 48.02; H, 3.88; S, 5.07.
Found: C, 47.92; H, 3.86; S, 4.82. FAB: m/z 1120 [M - ClO4]+.
[(dppb)P t(µ-EDT)Rh (CO)(P P h 3)]ClO4‚1/2CH2Cl2 (3f): yel-
low solid (68% yield). 1H NMR (300 MHz, CDCl3, 20 °C): δ
2.5-3.0 (m, 2 H, -CH2-, EDT), 1.6-2.0 (m, 2 H, -CH2-,
EDT), 7.0-7.8 (m, 35 H, Ph, dppb, PPh3), 2.5-3.0 (m, 4 H,
-PCH2-, dppb), 1.9-2.3 (m, 4 H, -CH2-, dppb). IR (KBr,
cm-1): ν(CO), 1984 (vs). Anal. Calcd for PtRhClS2P3O5C49H47‚1/
2CH2Cl2: C, 47.59; H, 3.84; S, 5.07. Found: C, 47.71; H, 3.83;
S, 5.11. FAB: m/z 1106 [M - ClO4]+.
[(d p p b )P t (µ-BDT)R h (CO)(P P h 3)]ClO4‚1/2CH 2Cl2 (3g):
yellow solid (70% yield). 1H NMR (300 MHz, CDCl3, 20 °C): δ
3.30 (m, 1 H, -SCH2-, BDT), 3.12 (m, 1 H, -SCH2-, BDT),
2.80 (m, 1 H, -SCH2-, BDT), 2.38 (m, 1 H, -SCH2-, BDT),
1.90 (m, 1 H, -CH2-, BDT), 1.60 (m, 1 H, -CH2-, BDT), 1.37
(m, 1 H, -CH2-, BDT), 1.10 (m, 1 H, -CH2-, BDT), 7.2-8.3
(m, 35 H, Ph, dppb and PPh3), 2.80 (m, 4 H, -PCH2-, dppb),
1.70 (m, 4 H, -CH2-, dppb). IR (KBr, cm-1): ν(CO), 1982 (vs).
Anal. Calcd for PtRhClS2P3O5C51H51‚1/2CH2Cl2: C, 48.43; H,
4.07; S, 5.01. Found: C, 48.63; H, 4.10; S, 4.93. FAB: m/z 1134
[M - ClO4]+.
Com p ou n d 2a ′: PtRhS2P2O2C40H34BF4‚1/2CH2Cl2, M )
1098.9, monoclinic, a ) 18.407 Å, R ) 90°, b ) 14.162 Å, â )
100.56°, c ) 32.693 Å, γ ) 90°, V ) 8378.2 Å3, space group
P21/c (14), Z ) 4, Dc ) 1.743 Mg/m3, F(000) ) 4288, purple,
crystal dimensions 0.22 × 0.15 × 0.18 mm, µ(Mo KR) ) 19.85
cm-1
.
Com p ou n d 3a : PtRhClS2P3O6C57H49‚CH2Cl2, M ) 1403.35,
triclinic, a ) 14.246 Å, R ) 81.75°, b ) 14.439 Å, â ) 81.06°,
c ) 14.519 Å, γ ) 83.15°, V ) 2905.4 Å3, space group P1h, Z )
2, Dc ) 1.604 Mg/m3, F(000) ) 1392, yellow, crystal dimensions
0.12 × 0.23 × 0.15 mm, µ(Mo KR) ) 14.67 cm-1
.
The XDS11 package was used to give the following: 7664
unique reflections [merging R ) 0.0266] (2a ′) and 5710 unique
reflections [merging R ) 0.0317] (3a ). The heavy atoms were
found from the Patterson map using the SHELX8612 program
and refined subsequently from successive difference Fourier
maps using SHELXL9313 by full-matrix least squares of 528
(2a ′) and 713 (3a ) variables, to a final R-factor of 0.0619 (2a ′)
and 0.0428 (3a ) for 7659 (2a ′) and 5705 (3a ) reflections with
[Fo] > 4σ(Fo). All atoms were revealed by the Fourier map
difference. Non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were placed geometrically and then refined
with fixed isotropic atomic displacement parameters. The
weighting scheme w ) 1/[σ2(Fo2) + (aP)2 + bP], where P ) max-
((Fo2, 0) + 2Fc2)/3, a ) 0.0846 (2a ′), 0.0523 (3a ) and b ) 115.82
(2a ′), 20.68 (3a ) with σ(Fo) from counting statistics, gave
satisfactory agreement analyses. The final parameters R1 ([Fo]
> 4σ(Fo)) were 0.0619 (2a ′) and 0.0428 (3a ), and wR2 (all data)
were 0.0777 (2a ′) and 0.0590 (3a ) for R1 ) ∑||Fo| - |Fc||/∑|Fo|
and wR2 ) [∑w(Fo - Fc2)/∑w(Fo2)2)]1/2. The ORTEP diagrams
2
for 2a ′ and 3a were generated using ORTEP-3.14
[(P P h 3)2P t(µ-EDT)Rh (CO)(P Cy3)]ClO4‚1/2CH2Cl2 (3h ):
yellow solid (79% yield). 1H NMR (300 MHz, CDCl3, 20 °C): δ
3.35 (m, 2 H, -CH2-, EDT), 2.88 (m, 1 H, -CH2-, EDT), 2.51
(m, 1 H, -CH2-, EDT), 7.2-7.6 (m, 30 H, Ph, PPh3), 1.1-1.9
(m, 33 H, -CH2-, PCy3). IR (KBr, cm-1): ν(CO), 1966 (vs).
Anal. Calcd for PtRhClS2P3O5C57H67‚1/2CH2Cl2: C, 50.58; H,
4.98; S, 4.69. Found: C, 50.48; H, 5.01; S, 4.09.FAB: m/z 1223
[MH - ClO4]+.
Resu lts a n d Discu ssion
cis-Dica r bon yl Com p lexes. The reaction of the
diolefin complexes [(P-P)Pt(µ-S-S)Rh(cod)]ClO4 (1a -
g) (P-P ) (PPh3)2, Ph2P(CH2)3PPh2 (dppp), and Ph2P-
(CH2)4PPh2 (dppb); S-S ) -S(CH2)2S- (EDT), -S(CH2)3S-
(PDT), -S(CH2)4S- (BDT), cod ) 1,5-cyclooctadiene,
Scheme 1) with carbon monoxide under atmospheric
pressure yielded the dicarbonyl complexes [(P-P)Pt(µ-
S-S)Rh(CO)2]ClO4 (2a -g, Scheme 1), which were iso-
lated in good yields.
The dinuclear framework was maintained in these
reactions as deduced from the spectroscopic data, which
confirmed the proposed formulations and revealed the
lack of bridge cleavage and ligand redistribution pro-
cesses. The m/z peaks of the cations were observed in
the FAB+ mass spectra, while the IR spectra showed
two ν(CO) bands separated by ca. 60 cm-1 as expected
[(P P h 3)2P t (µ-E DT)R h (CO)(P (Ot Bu P h )3)]ClO4‚1/2CH 2-
1
Cl2 (3i): yellow solid (88% yield). H NMR (300 MHz, CDCl3,
20 °C): δ 3.40 (m, 2 H, -CH2-, EDT), 2.97 (m, 1 H, -CH2-,
EDT), 2.51 (m, 1 H, -CH2-, EDT), 6.8-7.7 (m, 42 H, Ph, PPh3,
and P(OtBuPh)3), 1.30 (s, 27 H, -CH3, P(OtBuPh)3). IR (KBr,
cm-1): ν(CO), 2016 (vs). Anal. Calcd for PtRhClS2P3O8C69H73‚1/
2CH2Cl2: C, 53.39; H, 4.73; S, 4.09. Found: C, 53.12; H, 4.75;
S, 4.12. FAB: m/z 1421 [MH - ClO4]+, 915 [MH - (CO) -
P(OtBuPh)3 - ClO4]+.
P r ep a r a t ion
of Com p lex [(P P h 3)2P t (µ-E DT)R h -
(P (OP h )3)2]ClO4‚1/2CH2Cl2 (4). Carbon monoxide was bubbled
for 10 min through a dichloromethane solution of the corre-
sponding diene complex 1a (0.05 mmol in 5 mL of solvent) to
form the corresponding carbonyl complex. Then, P(OPh)3 (0.10
mmol) was added and the solution was stirred for 10 min. The
solution was concentrated to 2 mL, and hexane was added to
give a yellow precipitate (79% yield). The solid was filtered,
(11) Kabsch, W. J . Appl. Crystallogr. 1993, 26, 795.
(12) Sheldrick, G. M. SHELXS-86: Program for Crystal Structure
Solutions; University of Go¨ttingen: Germany, 1986.
(13) Sheldrick, G. M. SHELXS-93: Program for Crystal Structure
Solutions; University of Go¨ttingen: Germany, 1993.
(14) Farrugia, L. J . ORTEP-3 for Windows. J . Appl. Crystallogr.
1997, 30, 565.
1
washed with hexane, and vacuum-dried. H NMR (300 MHz,
CDCl3, 20 °C): δ 2.68 (m, 2 H, -CH2-, EDT), 1.40 (m, 2 H,