Synthesis and structures of heterodinuclear organoplatinum(or -palladium)-molybdenum(or -tungsten) complexes: Unexpected structural deformation of heterodinuclear propionylplatinum-tungsten complex having 1,2-bis(diphenylphosphino)ethane ligand

Article abstract of DOI:10.1016/j.ica.2005.12.026

Synthesis of a series of heterodinuclear phenylpalladium-molybdenum(or -tungsten) complexes having a bidentate nitrogen ligand, L₂PhPd-MCp(CO)₃ (M = Mo, L₂ = tmeda (12), bpy (13), phen (14); M = W, L₂ = tmeda (15)) by metathetical reactions of PdPhIL₂ with Na[MCp(CO)₃] and acylplatinum-molybdenum(or -tungsten) complex having a 1,2-bis(diphenylphosphino)ethane ligand, (dppe)(RCO)Pt-MCp(CO)₃ (M = Mo, R = Et (16), CH₂CMe₃ (18); M = W, R = Et (17)) by CO insertion into Pt-C bond in corresponding alkyl analogues (dppe)RPt-MCp(CO)₃ (M = Mo, R = Et (6), CH₂CMe₃, M = W, R = Et (8)) are described. These complexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 12, 13, 17 and 18 are determined by X-ray structure analysis. The geometry at Pt (or Pd) is square planar and the MCp(CO)₃ moiety has three-leg piano-stool geometries in these complex expect the propionylplatinum-tungsten complex 17, which shows apparent but unexpected structural deformation at Pt and W, giving twisted square-planar and four-leg piano-stool geometries for platinum and tungsten, respectively.

Full text of DOI:10.1016/j.ica.2005.12.026

Inorganica Chimica Acta 359 (2006) 3699–3708
www.elsevier.com/locate/ica
Synthesis and structures of heterodinuclear organoplatinum(or
-palladium)–molybdenum(or -tungsten) complexes:
Unexpected structural deformation of heterodinuclear
propionylplatinum–tungsten complex having
1,2-bis(diphenylphosphino)ethane ligand
Nobuyuki Komine, Susumu Tsutsuminai, Hideko Hoh, Toshiyuki Yasuda,
*
Masafumi Hirano, Sanshiro Komiya
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei,
Tokyo 184-8588, Japan
Received 13 November 2005; received in revised form 2 December 2005; accepted 6 December 2005
Available online 19 January 2006
Dedicated to Professor D. Michael P. Mingos on his great contribution to organometallic chemistry.
Abstract
Synthesis of a series of heterodinuclear phenylpalladium–molybdenum(or -tungsten) complexes having a bidentate nitrogen ligand,
L2PhPd–MCp(CO)3 (M = Mo, L2 = tmeda (12), bpy (13), phen (14); M = W, L2 = tmeda (15)) by metathetical reactions of PdPhIL2
with Na[MCp(CO)3] and acylplatinum–molybdenum(or -tungsten) complex having a 1,2-bis(diphenylphosphino)ethane ligand,
(dppe)(RCO)Pt–MCp(CO)3 (M = Mo, R = Et (16), CH2CMe3 (18); M = W, R = Et (17)) by CO insertion into Pt–C bond in corre-
sponding alkyl analogues (dppe)RPt–MCp(CO)3 (M = Mo, R = Et (6), CH2CMe3, M = W, R = Et (8)) are described. These com-
plexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 12, 13, 17 and 18
are determined by X-ray structure analysis. The geometry at Pt (or Pd) is square planar and the MCp(CO)3 moiety has three-leg
piano-stool geometries in these complex expect the propionylplatinum–tungsten complex 17, which shows apparent but unexpected
structural deformation at Pt and W, giving twisted square-planar and four-leg piano-stool geometries for platinum and tungsten,
respectively.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Heterodinuclear organometallic complexes; Organoplatinum-molybdenum complexes; Organoplatinum-tungsten complexes; Organopalla-
dium-molybdenum complex; Organopalladium-tungsten complex; X-ray crystal structure
1. Introduction
tions in relation to heterobimetallic catalysis [1,2]. We
previously reported the synthesis of such complexes
L2RM–M0L0n (M = Pt, Pd, Ni; M0 = Mo, W, Mn, Re, Fe,
Co; R = Me, Et, CH2CMe3, Ph, COMe, H; L2 = cod
(1,5-cyclooctadiene), dppe (1,2-bis(diphenylphosphino)-
ethane), tmeda (N,N,N0,N0-tetramethylethylenediamine),
Heterodinuclear organometallic complexes having both
M–M0 and M–C bonds have attracted considerable atten-
tion due to their possible synergism in structure and reac-
bpy
(2,20-bipyridine),
phen
(1,10-phenanthroline),
Ph2PC2-H4NEt2; L0 = CO, Cp), which showed unique reac-
tions [3] and notable catalytic activity [4]. For example, the
*
Corresponding author.
E-mail address: komiya@cc.tuat.ac.jp (S. Komiya).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.12.026

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N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
heterodinucler organoplatinum–molybdenum(or -tungsten)
complexes having 1,5-cyclooctadiene ligand, (cod)RPt–
MCp(CO)3 (M = Mo, R = Me (1), Ph (2), M = W,
R = Me (3), Ph (4)) show specific organic group transfer
between different metal centers [3a,3c]. We also reported
the synthesis of organoplatinum–molybdenum(or -tung-
sten) complex with a dppe ligand, (dppe)RPt–MCp(CO)3
(M = Mo, R = Me (5), Et (6), M = W, R = Me (7), Et
(8)) [3d,3e]. Thermolysis of ethylplatinum–molybdenum
or -tungsten complexes 6 and 8 induced significant acceler-
ation of b-H elimination to give hydrideplatinum–molybde-
num or -tungsten complex [3e]. The synthesis and reactivity
of palladium derivatives, (dppe)MePd–MLn (MLn =
MoCp(CO)3 (9), WCp(CO)3 (10), Co(CO)4 (11)) also were
previously described [3f,3j]. The methylpalladium–cobalt
complex (11) shows a high activity of CO insertion, giving
(dppe)(MeCO)Pd–Co(CO)4, and initial rate is ca. 80 times
higher than that of the analogue complex PdMeCl(dppe).
Ligand effect on structure and reactivity of these heterodi-
nuclear complexes are our continuing general interests in
this chemistry. In the present study, we investigated synthe-
sis and structure of various heterodinuclear organoplati-
num(or -palladium)–molybdenum(or -tungsten) complex,
L2RM–M0Cp(CO)3 (M = Pt, Pd; M0 = Mo, W; R = phe-
nyl, acyl; L2 = dppe, tmeda, bpy, phen). As a result, we
found apparent but unexpected structural deformation of
geometries both at Pt and W in the propionylplatinum–
tungsten complex having 1,2-bis(diphenylphosphino)eth-
ane, toward twisted square-planar Pt and four-leg
piano-stool W.
ð1Þ
Heterodinuclear methyl(or ethyl)platinum–molybde-
num(or -tungsten) complexes with dppe ligand,
(dppe)RPt–MCp(CO)3 (M = Mo, R = Me (5), Et (6),
M = W, R = Me (7), Et (8)) were prepared by the meta-
thetical reaction of PtR(NO3)(dppe) with Na[MCp(CO)3]
[3d,3e]. Corresponding acyl complexes, (dppe)(EtCO)Pt–
MoCp(CO) (16), and (dppe)(EtCO)Pt–WCp(CO)3 (17)
were prepared by the treatment of 6 and 8 with CO
(1 atm) at room temperature in 38% and 34% yields,
respectively (Eq. (2)). On the other hand, methyl deriva-
tives were reluctant to the CO insertion under these condi-
tions. (dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18) was also
prepared by the metathetical reactions of Pt(CH2CMe3)-
(NO3)(dppe) with Na[MoCp(CO)3] followed by treatment
with CO
ð2Þ
These novel dinuclear organopalladium(or -platinum)
complexes (12–18) were characterized by 1H NMR and
IR spectroscopies and elemental analysis as well as by X-
ray structure analysis (vide infra). Selected IR and 1H
NMR data of 12–18 and the related complexes are summa-
rized in Tables 1 and 2.
2. Results and discussion
2.1. Synthesis of heterodinuclear organoplatinum(or
-palladium)–molybdenum(or -tungsten) complexes
The IR spectra of dinuclear phenylpalladium com-
plexes (12–15) exhibited m(CO) bands between approxi-
mately 1750 and 1900 cmꢀ1 due to terminal and
bridging carbonyls, whose frequencies were similar to
that for Na[MCp(CO)3] (M = Mo, W) (Table 1). These
data suggest that the back-bonding from Mo (or W) to
CO is strong. 1H NMR spectrum of 12 shows two
methyl resonances and two methylene resonances for
TMEDA at ambient temperature, indicating square pla-
nar geometry at Pd. Similarly to (dppe)MePd–MCp(CO)3
(M = Mo (9), W (10)), the oxidation state of the metals
are expected to be close to Pd(II) and Mo(0) (or
W(0)). The novel dinuclear acylplatinum complexes (16–
At first, we investigated synthesis of heterodinuclear
organopalladium–molybdenum(or -tungsten) complexes
having a bidentate nitrogen ligand such as N,N,N0,N0-
tetramethylethylenediamine, 2,20-bipyridine and 1,10-
phenanthroline ligand. Heterodinuclear phenylpalladium–
molybdenum(or -tungsten) complexes having a bidentate
nitrogen ligand, L2PhPd–MCp(CO)3 (M = Mo, L2 =
tmeda (12), bpy (13), phen (14); M = W, L2 = tmeda
(15)) were synthesized by simple metathetical reactions of
PdPh(NO3)L2, which was prepared in situ from PdPhIL2
[5] and AgNO3, with the transition-metal anions Na[MCp-
(CO)3] [6] in THF (Eq. (1)). On the other hand, the reaction
of PdMeIL2 (L2 = tmeda, bpy, phen) with Na[MoCp-
(CO)3] was unsuccessful, and gave methylmolybdenum
complex MoMeCp(CO)3 with a nitrogen bidentate ligand
accompanied by formation of Pd black. This methylmolyb-
denum complex may be formed via the formation of
heterodinucler methylpalladium complexes, L2MePd–Mo-
Cp(CO)3, following by methyl transfer from Pd to Mo
[3f,3j]
1
18) were also characterized by H NMR and IR spectros-
copy (Table 2) and elemental analysis as well as by X-ray
structure analysis (vide infra). 31P{1H} NMR spectra of
16–18 display two inequivalent signals with Pt satellites
2
with small JP–P coupling constant (0–7 Hz), which is
consistent with the square planar cis structure of these
complexes. IR spectra of these complexes display
m(C@O) bands of the PtCOR group at 1630 cmꢀ1 and

N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
3701
Table 1
Selected IR and 1H NMR data of heterodinuclear phenylpalladium–molybdenum(or -tungsten) complex with a bidentete nitrogen ligand
Complex
IR (mCO, cmꢀ1 a
)
1H NMR (ppm)b
Cp
Ph
L2
(tmeda)PhPd–MoCp(CO)3 (12)
1879 (s)
1783 (vs)
4.67 (s, 5H)
7.30 (d, JHH = 7.2 Hz, 2H, o-C6H5)
6.96 (t, JHH = 7.2 Hz, 2H, m-C6H5)
6.80 (t, JHH = 7.2 Hz, 1H, m-C6H5)
2.9 (brs, 2H, CH2)
2.7 (brs, 2H, CH2)
2.42 (s, 2H, CH3)
2.22 (s, 2H, CH3)
8.8 (brs, 1H, H6)
8.6 (brs, H3, H30)
8.24 (t, JHH = 8.1 Hz, 2H, H4, H40)
7.8 (brs, 1H, H5 or H50)
7.6 (brs, 1H, H5 or H50)
7.4 (brs, 1H, H60)
(bpy)PhPd–MoCp(CO)3 (13)
(phen)PhPd–MoCp(CO)3 (14)
1901 (s)
1789 (s)
1780 (s)
4.83 (s, 5H)
4.87 (s, 5H)
4.71 (s, 5H)
7.37 (dt, JHH = 7.2, 1.5 Hz, o-C6H5)
7.07 (tt, JHH = 7.2, 1.5 Hz, m-C6H5)
6.89 (tt, JHH = 7.2, 1.5 Hz, m-C6H5)
1985 (s)
1806 (s)
1780 (s)
7.44 (dt, JHH = 7.5, 1.2 Hz, 1H, o-C6H5)
7.14 (tt, JHH = 7.5, 1.2 Hz, 2H, m-C6H5)
6.95 (tt, JHH = 7.5, 1.2 Hz, 2H, p-C6H5)
9.1 (brs, 1H, H2)
8.83 (d, JHH = 7.8 Hz, 2H, H3, H8)
8.24 (s, 2H, H5, H6)
8.1 (brs, 1H, H4)
7.9 (brs, 1H, H7)
7.7 (brs, 1H, H9)
(tmeda)PhPd–WCp(CO)3 (15)c
1875 (s)
1775 (vs)
7.35 (m, 2H, o-C6H5)
6.96 (tt, JHH = 7.2, 1.5 Hz, 2H, m-C6H5)
6.78 (tt, JHH = 7.2, 1.5 Hz, 1H, p-C6H5)
2.86 (brs, 2H, CH2)
2.72 (brs, 2H, CH2)
2.38 (brs, 6H, CH3)
2.18 (brs, 6H, CH3)
a
IR spectra were measured by KBr pellet method.
b
c
1H NMR spectra were measured in acetone-d6 at room temperature.
1H NMR spectra were measured in acetone-d6 at ꢀ40 ꢁC.
Table 2
Selected IR and NMR data for heterodinuclear organoplatinum(-palladium) complex with 1,2-bis(diphenylphosphino)ethane
Complex
IR (mCO, cmꢀ1 a
)
Cp
1H NMR (ppm)b, R
31P NMR (ppm)b
(dppe)MePt–MoCp(CO)3 (5)
1907 (s)
1795 (s)
1902 (s)
4.63 (s, 5H) 1.44 (t, JPH = 6.1 Hz, JPtH = 59.7 Hz,
61.20 (s, JPtP = 3446 Hz)
43.68 (s, JPtP = 1742 Hz)
2H, CH2)
(dppe)EtPt–MoCp(CO)3 (6)
4.67 (s, 5H) 2.23 (sextet, JPH = 11 Hz, JHH = 11 Hz, 59.01 (s, JPtP = 3711 Hz)
JPtH = 69 Hz, 2H, CH2)
1788 (s)
1922 (s)
1818 (s)
1628 (s)
1.32 (dt, JPH = 11 Hz, JHH = 11 Hz,
3H, CH3)
5.04 (s, 5H) 2.52 (m, 3H, CH2)
39.59 (s, JPtP = 1487 Hz)
(dppe)(EtCO)Pt–MoCp(CO)3 (17)
39.22 (d, JPP = 5 Hz,
JPtP = 1456 Hz)
34.88 (d, JPP = 5 Hz,
JPtP = 3577 Hz)
0.79 (t, JHH = 7.2 Hz, 3H, CH3)
(dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18) 1911 (s)
5.05 (s, 5H) 2.87 (s, 2H, CH2)
35.84 (s, JPtP = 1360 Hz)
32.73 (s, JPtP = 3687 Hz)
1803 (s)
0.87 (s, 9H, CH3)
1639 (m)
(dppe)MePt–WCp(CO)3 (7)
(dppe)EtPt–WCp(CO)3 (8)
1894 (s)
1797 (s)
1782 (s)
1899 (s)
4.59 (s, 5H) 1.64 (t, JPH = 6.8 Hz, JPtH = 57.6 Hz,
62.66 (s, JPtP = 3395 Hz)
44.31 (s, JPtP = 1731 Hz)
2H, CH2)
4.61 (s, 5H) 2.41 (sextet, JPH = 8 Hz, JHH = 8 Hz,
JPtH = 71 Hz, 2H, CH2)
1.35 (dt, JPH = 9 Hz, JHH = 8 Hz, 3H,
CH3)
5.03 (s, 5H) 2.53 (m, 2H, CH2)
60.47 (s, JPtP = 3633 Hz)
40.32 (s, JPtP = 1485 Hz)
1789 (s)
1924 (s)
1832 (s)
(dppe)(EtCO)Pt–WCp(CO)3 (17)
41.43 (d, JPP = 5 Hz,
JPtP = 1463 Hz)
34.88 (d, JPP = 7 Hz,
JPtP = 3302 Hz)
0.85 (t, JHH = 7.2 Hz, 3H, CH3)
1801 (s)
1629 (s)
1901 (s)
1792 (s)
1893 (s)
1785 (s)
(dppe)MePd–MoCp(CO)3 (10)
4.69 (s, 5H) 1.52 (dd, JPH = 7.8, 6.0 Hz, 3H, CH3)
4.64 (s, 5H) 1.69 (t, JPH = 6.9 Hz, 3H, CH3)
56.8 (d, JPP = 18 Hz)
35.4 (d, JPP = 18 Hz)
60.7 (d, JPP = 18 Hz)
38.2 (d, JPP = 18 Hz)
(dppe)MePd–WCp(CO)3 (11)
a
IR spectra were measured by KBr pellet method.
NMR spectra were measured in C6D6 at room temperature.
b

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N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
Table 3
Crystallographic data for (tmeda)PhPd–MoCp(CO)3 (12), (bpy)PhPd–MoCp(CO)3 (13), and (tmeda)PhPt–MoCp(CO)3 (20)
12
13
20
Empirical formula
Formula weight
Crystal color, habit
Crystal dimension (mm)
Crystal system
C
544.78
orange, cubic
0.22 · 0.18 · 0.14
monoclinic
P21/n
20H26N2O3MoPd
C24H18N2O3MoPd
584.76
red, cubic
0.40 · 0.35 · 0.31
monoclinic
P21/a
C20H26N2O3MoPt
633.47
orange, prismatic
0.25 · 0.17 · 0.08
monoclinic
P21/n
Space group
˚
a (A)
8.350(6)
15.044(6)
16.940(8)
93.69(6)
2123(1)
13.288(3)
12.237(5)
13.562(6)
94.47(3)
8.304(6)
15.023(8)
16.958(9)
93.27(6)
2112(2)
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
2198(1)
Z
4
4
4
DCalc (g cmꢀ3
F(000)
)
1.704
1088.00
14.58
1.767
1152.00
13.91
1.992
1216.00
72.04
l (Mo Ka) (cmꢀ1
)
Diffractometer
Rigaku AFC7R
0.71069
ꢀ160.0
Rigaku AFC5R
0.71069
room temperature
x–2h
Rigaku AFC7R
0.71069
˚
Radiation (A)
Temperature (ꢁC)
Scan type
ꢀ33.0
x
x–2h
2hmax (ꢁ)
Number of reflection measured
55.0
54.9
55.0
total: 5196
unique: 4871
2441
total: 5245
unique: 5203
2368
total: 5363
unique: 4835
2693
Number of observation (I > 3.00r(I))
Structure solution
Patterson method
(DIRDIF 94 PATTY)
0.042
Patterson method
(DIRDIF 94 PATTY)
0.045
Direct methods
(SAPI 91)
0.036
Ra
b
Rw
0.060
0.050
0.045
Goodness-of-fit indicator
1.17
1.08
1.06
a
R = R(iFo| ꢀ |Fci)/R|Fo|.
b
Rw = [Rw(|Fo| ꢀ |Fc|)2/Rw|Fo|2]0.5
.
Table 4
Crystallographic data for (dppe)MePt–WCp(CO)3 (7), (dppe)(EtCO)Pt–WCp(CO)3 (17), and (dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18)
7 Æ C4H8O
39H40O4P2PtW
17 Æ C6H6
18 Æ C3H6O
Empirical formula
Formula weight
Crystal color, habit
Crystal dimension (mm)
Crystal system
C
C43H40O4P2PtW
1061.67
orange, plates
0.93 · 0.40 · 0.27
triclinic
C40H40MoO4P2Pt
937.73
orange, prismatic
0.40 · 0.35 · 0.31
triclinic
1013.63
yellow, prismatic
0.39 · 0.31 · 0.17
monoclinic
P21/a
17.996(10)
11.223(5)
ꢀ
ꢀ
Space group
P1
P1
˚
a (A)
13.582(5)
16.877(9)
11.141(3)
100.96(5)
108.90(3)
71.43(4)
2279(1)
12.640(4)
16.056(7)
12.154(5)
110.18(3)
115.95(3)
82.98(3)
2080(1)
˚
b (A)
˚
c (A)
19.528(7)
a (ꢁ)
b (ꢁ)
c (ꢁ)
93.34(4)
3
˚
V (A )
3937(2)
4
1.710
1952.00
65.74
Z
2
2
DCalc (g cmꢀ3
F(000)
)
1.547
1024.00
56.82
1.589
988.00
37.64
l (Mo Ka) (cmꢀ1
)
Diffractometer
Rigaku AFC7R
0.71069
ꢀ33.0
Rigaku AFC5R
0.71069
room temperature
x–2h
Rigaku AFC7R
0.71069
ꢀ33.0
˚
Radiation (A)
Temperature (ꢁC)
Scan type
x–2h
x–2h
2hmax (ꢁ)
Number of reflection measured
55.0
55.1
55.0
total: 9789
unique: 9028
5971
total: 10987
unique: 10544
7009
total: 9981
unique: 9545
7422
Number of observation (I > 3.00r(I))
Structure solution
Direct methods
(SAPI 91)
0.082
Direct methods
(SAPI 91)
0.042
Patterson method
(DIRDIF 94 PATTY)
0.031
Ra
b
Rw
0.110
0.067
0.041
Goodness-of-fit indicator
1.04
1.00
1.12
a
R = R(iFo| ꢀ |Fci)/R|Fo|.
b
Rw = [Rw(|Fo| ꢀ |Fc|)2/Rw|Fo|2]0.5
.

N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
3703
m(C„O) bands between approximately 1800 and 1900
cmꢀ1, which were shifted to higher frequencies in com-
parison with corresponding alkyl complexes 5–8, imply-
ing weaker back-bonding from Mo (or W) to CO.
Furthermore, the resonance for Cp protons in 16–18
was shifted to downfield in comparison with correspond-
ing alkyl complexes in their 1H NMR spectra. These
trend may be interpreted by a lower electron density at
Mo (or W) of 16–18 than alkyl complexes 5–8, due to
stronger electron withdrawing property of the acyl ligand
on platinum metal.
CO)Pt–WCp(CO)3 (17) with methyl iodide in CD2Cl2
gave WMeCp(CO)3 (77%) and Pt(COEt)I(dppe) (80%),
but no WICp(CO)3 and Pt(COMe)(Me)(dppe) (Eq. (3)).
Similar result was obtained for the reaction of ethyl deriv-
ative 8 with MeI. These results indicate that Pt is essen-
tially electrophilic and W is nucleophilic in both cases,
being consistent with Pt(II)/W(0) formalism rather than
Pt(0)/W(II)
In order to clarify the polarization of metal–metal
bond, reactions of heterodinuclear complex with electro-
phile such as methyl iodide was investigated. Reaction
of propionylplatinum–tungsten complex, (dppe)(Et-
ð3Þ
Table 6
Selected bond lengths and bond angles for (dppe)MePt–WCp(CO)3 (7),
(dppe)(EtCO)Pt–WCp(CO)3 (17) and (dppe)(Me3CCH2CO)Pt–MoCp-
(CO)3 (18)
Table 5
Selected bond lengths and bond angles for (tmeda)PhPd–MoCp(CO)3
(12), (bpy)PhPd–MoCp(CO)3 (13) and (tmeda)PhPt–MoCp(CO)3 (20)
˚
Bond lengths (A) for (dppe)MePt–WCp(CO)3 (7)
˚
Bond lengths (A) for (tmeda)PhPd–MoCp(CO)3 (12)
Pt(1)–W(1)
Pt(1)–P(1)
Pt(1)–C(28)
W(1)–C(28)
W(1)–C(30)
C(29)–O(2)
2.929(1)
2.239(4)
2.37(2)
2.00(1)
1.99(2)
1.16(2)
Pt(1)–C(1)
Pt(1)–P(2)
Pt(1)–C(30)
W(1)–C(29)
C(28)–O(1)
C(30)–O(3)
2.13(2)
2.318(4)
2.57(1)
1.94(2)
1.18(2)
1.16(2)
Pd(1)–Mo(1)
Pd(1)–N(1)
Pd(1)–C(13)
Mo(1)–C(13)
Mo(1)–C(15)
C(14)–O(2)
2.795(1)
2.208(8)
2.313(9)
1.978(10)
1.98(1)
Pd(1)–C(1)
Pd(1)–N(2)
Pd(1)–C(15)
Mo(1)–C(14)
C(13)–O(1)
C(15)–O(3)
1.994(9)
2.297(8)
2.368(9)
1.94(1)
1.17(1)
1.18(1)
1.15(1)
Bond angles (ꢁ) for (dppe)MePt–WCp(CO)3 (7)
Bond angles (ꢁ) for (tmeda)PhPd–MoCp(CO)3 (12)
W(1)–Pt(1)–C(1)
C(1)–Pt(1)–P(1)
W(1)–C(28)–O(1)
W(1)–C(30)–O(3)
Pt(1)–Mo(1)–C(29)
91.6(5)
85.1(5)
161(2)
169(1)
103.7(6)
W(1)–Pt(1)–P(2)
P(1)–Pt(1)–P(2)
W(1)–C(29)–O(2)
Pt(1)–W(1)–C(28)
Pt(1)–W(1)–C(30)
97.38(9)
86.0(2)
178(2)
53.4(5)
59.3(4)
Mo(1)–Pd(1)–C(1)
83.5(2)
Mo(1)–Pd(1)–N(2)
105.7(2)
C(1)–Pd(1)–N(1)
90.7(3)
N(1)–Pd(1)–N(2)
80.2(3)
175.4(10)
54.8(3)
Mo(1)–C(13)–O(1)
Mo(1)–C(15)–O(3)
Pd(1)–Mo(1)–C(14)
164.5(8)
166.4(8)
98.7(3)
Mo(1)–C(14)–O(2)
Pd(1)–Mo(1)–C(13)
Pd(1)–Mo(1)–C(15)
56.4(3)
˚
Bond lengths (A) for (dppe)(EtCO)Pt–WCp(CO)3 (17)
˚
Bond lengths (A) for (bpy)PhPd–MoCp(CO)3 (13)
Pt(1)–W(1)
Pt(1)–P(1)
Pt(1)–C(30)
W(1)–C(30)
W(1)–C(32)
C(31)–O(3)
2.8940(6)
2.248(3)
2.62(1)
1.950(9)
1.94(1)
Pt(1)–C(1)
Pt(1)–P(2)
Pt(1)–C(32)
W(1)–C(31)
C(30)–O(2)
C(32)–O(4)
2.055(9)
2.348(2)
2.71(1)
1.96(1)
1.19(1)
1.15(2)
Pd(1)–Mo(1)
Pd(1)–N(1)
Pd(1)–C(17)
Mo(1)–C(17)
Mo(1)–C(19)
C(18)–O(2)
2.793(1)
2.161(7)
2.34(1)
1.98(1)
1.97(1)
1.17(1)
Pd(1)–C(1)
Pd(1)–N(2)
Pd(1)–C(19)
Mo(1)–C(18)
C(17)–O(1)
C(19)–O(3)
1.975(10)
2.178(8)
2.398(9)
1.90(1)
1.16(1)
1.17(1)
1.13(1)
Bond angles (ꢁ) for (dppe)(EtCO)Pt–WCp(CO)3 (17)
Bond angles (ꢁ) for (bpy)PhPd–MoCp(CO)3 (13)
W(1)–Pt(1)–C(1)
C(1)–Pt(1)–P(1)
W(1)–C(30)–O(2)
W(1)–C(32)–O(4)
Pt(1)–W(1)–C(31)
86.3(3)
87.0(4)
171(1)
172.0(9)
119.5(4)
W(1)–Pt(1)–P(2)
P(1)–Pt(1)–P(2)
W(1)–C(31)–O(3)
Pt(1)–W(1)–C(30)
Pt(1)–W(1)–C(32)
106.37(7)
84.64(9)
177(1)
61.9(4)
64.8(3)
Mo(1)–Pd(1)–C(1)
81.6(3)
Mo(1)–Pd(1)–N(2)
108.8(2)
75.8(3)
178(1)
55.7(3)
57.4(3)
C(1)–Pd(1)–N(1)
93.8(3)
N(1)–Pd(1)–N(2)
Mo(1)–C(17)–O(1)
Mo(1)–C(19)–O(3)
Pd(1)–Mo(1)–C(18)
167.1(9)
169.7(8)
105.4(3)
Mo(1)–C(18)–O(2)
Pd(1)–Mo(1)–C(17)
Pd(1)–Mo(1)–C(19)
˚
Bond lengths (A) for (dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18)
˚
Bond lengths (A) for (tmeda)PhPt–MoCp(CO)3 (20)
Pt(1)–Mo(1)
Pt(1)–P(1)
Pt(1)–C(33)
Mo(1)–C(33)
Mo(1)–C(35)
C(34)–O(3)
2.9300(9)
2.278(2)
2.509(6)
1.981(6)
1.962(6)
1.153(8)
Pt(1)–C(1)
Pt(1)–P(2)
Pt(1)–C(35)
Mo(1)–C(34)
C(33)–O(2)
C(35)–O(4)
2.077(5)
2.379(1)
2.557(6)
1.940(7)
1.158(7)
1.173(7)
Pt(1)–Mo(1)
Pt(1)–N(1)
Pt(1)–C(13)
Mo(1)–C(13)
Mo(1)–C(15)
C(14)–O(2)
2.806(1)
2.194(9)
2.32(1)
1.96(1)
1.98(1)
1.18(1)
Pt(1)–C(1)
Pt(1)–N(2)
Pt(1)–C(15)
Mo(1)–C(14)
C(13)–O(1)
C(15)–O(3)
2.02(1)
2.247(9)
2.40(1)
1.92(1)
1.18(1)
1.17(1)
Bond angles (ꢁ) for (dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18)
Bond angles (ꢁ) for (tmeda)PhPt–MoCp(CO)3 (20)
Mo(1)–Pt(1)–C(1)
90.2(2)
Mo(1)–Pt(1)–P(2)
95.65(3)
85.01(4)
176.2(7)
57.6(2)
Mo(1)–Pd(1)–C(1)
84.6(3)
Mo(1)–Pt(1)–N(2)
102.9(3)
81.4(4)
176(1)
55.0(3)
57.1(3)
C(1)–Pt(1)–P(1)
89.1(2)
P(1)–Pt(1)–P(2)
C(1)–Pt(1)–N(1)
91.1(4)
N(1)–Pt(1)–N(2)
Mo(1)–C(33)–O(2)
Mo(1)–C(35)–O(4)
Pt(1)–Mo(1)–C(34)
167.7(6)
166.7(5)
102.5(2)
Mo(1)–C(34)–O(3)
Pt(1)–Mo(1)–C(33)
Pt(1)–Mo(1)–C(35)
Mo(1)–C(13)–O(1)
Mo(1)–C(15)–O(3)
Pt(1)–Mo(1)–C(14)
164.7(9)
166.8(9)
99.6(3)
Mo(1)–C(14)–O(2)
Pt(1)–Mo(1)–C(13)
Pt(1)–Mo(1)–C(15)
59.1(2)

3704
N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
2.2. Molecular structure of heterodinuclear
organoplatinum(or- palladium)–molybdenum(or -tungsten)
complexes
W) bond distances in organoplatinum–molybdenum-
(or -tungsten) complexes are approximately 2.9 A, which
˚
is similar to reported other dinuclear platinum–molybde-
num(or tungsten) complex, 2, 4 and 19 [3b,3c,3k]. The
geometry around Pt (or Pd) in organoplatinum(or -palla-
dium)–molybdenum complexes is square planar, and the
Mo has a three-leg piano-stool type (tetrahedral) structure.
For example, the Pd(1), Mo(1), C(1), N(1) and N(2) in 12
are deviated from their mean least square plane within
We previously reported the molecular structure of sev-
eral organoplatinum–molybdenum(or -tungsten) com-
plexes, such as (cod)PhPt–MCp(CO)3 (M = Mo(2), W(4))
[3b,3c] and (Ph2PC2H4NEt2)PhPt–MoCp(CO)3 (19) [3k].
In this work, the molecular structures of novel acylplati-
num–molybdenum(or -tungsten) complexes, (dppe)(R-
CO)Pt–MCp(CO)3 (M = W, R = Et (17), M = Mo,
R = CH2CMe3 (18)) and phenylpalladium–molybdenum
complexes, L2PhPd–MoCp(CO)3 (L2 = tmeda (12), bpy
(13)) were determined by single-crystal structure analysis.
The structure determinations of related organoplatinum
complexes, (dppe)MePt–WCp(CO)3 (7) and (tmeda)PhPt–
MoCp(CO)3 (20) were also performed. The crystallo-
graphic data and selected bond distances and bond angles
are summarized in Tables 3–6, and ORTEP drawings are
depicted in Figs. 1 and 2.
˚
0.19 A, and the Mo moiety possesses pseudo C3v symmetry.
It is known that Mo(0) anionic complex [MoCp(CO)3]ꢀ
has a three-leg piano-stool type (tetrahedral) structure [8],
but Mo(II) complexes [9] such as MoClCp(CO)2(Ph2PN-
(Me)CH(Me)(Ph)) [9b] and MoClCp(CO)3 [9c] usually
have a four-leg piano-stool type (square pyramidal) struc-
ture. The IR data also support these electronic configura-
tions (vide supra). These structural features around both
metals are consistent with the electronic configurations of
d8-Pt(II) (or Pd(II)) and d6-Mo(0). It is notable that two
of carbonyl ligands of Mo coordinate to the Pt (or Pd) giv-
ing semibridging feature: the Mo(1)–C(13)–O(1) [164.5(8)]
and Mo(1)–C(15)–0(2) [166.4(8)] of 12 linkages are slightly
bent, and Pd(1), Mo(1), C(13), and C(15) are located
in same plane. Similarly, the geometry around Pt in
The Pd–Mo bond distances for phenylpalladium–
˚
molybdenum complexes 12 and 13 (2.795 and 2.793 A) fall
within the range observed for other dinuclear palladium–
˚
molybdenum complex (2.93–2.69 A) [7]. The Pt–Mo (or
Fig. 1. ORTEP drawings of (tmeda)PhPd–MoCp(CO)3 (12), (bpy)PhPd–MoCp(CO)3 (13) and (tmeda)PhPt–MoCp(CO)3 (20). The methylene C atoms of
TMEDA of 12 and 20 have been found disordered: the higher weight conformer is shown here. All hydrogen atoms and solvent are omitted for clarity.
Ellipsoids represent 50% probability.

N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
3705
Fig. 2. ORTEP drawings of (dppe)MePt–WCp(CO)3 (7), (dppe)(EtCO)Pt–WCp(CO)3 (17), and (dppe)(Me3CCH2CO)Pt–MoCp(CO)3 (18). All hydrogen
atoms and solvent are omitted for clarity. Ellipsoids represent 50% probability.
methylplatinum–tungsten complex 7 is square planar; the
Pt(1), W(1), C(1), P(1), and P(2) atoms are in the plane,
where deviations from their least square plane are within
mined organopalladium(or -platinum) complexes (14–30ꢁ)
(Table 7). The W(1)–C(30)–O(2) [172(1)ꢁ] and W(1)–
C(32)–O(4) [172.0(9)ꢁ] linkages in 17 are linear as
compared with corresponding linkages of other plati-
num–tungsten complexes (161–169ꢁ), suggesting these two
CO ligands have little bridging interaction with Pt. These
structural features around both metals are consistent with
the electronic configurations of d10-Pt(0) and d4-Mo(II).
It should also be noted that other structurally determined
heterodinuclear organoplatinum–tungsten(or -molybde-
num) complexes and palladium derivatives show no such
large distortion around the Pt (or Pd) metal center
[3b,3c,3k]. Failure to observe such distortion in the analo-
gous acylplatinum–molybdenum complex 18 suggests that
stronger electron withdrawing property of the acyl ligand
in comparison with the alkyl ligand is not the origin of this
structural deformation. Therefore, the present distortion of
˚
0.20 A, and the W has a three-leg piano-stool type struc-
ture. However, unexpectedly, geometry at Pt of the propi-
onylplatinum–tungsten complex 17 was highly distorted,
giving a large dihedral angle of 24.2ꢁ between Pt(1)–P(1)–
P(2) and Pt(1)–C(1)–W(1) planes, whereas geometries
at Pt (or Pd) of other structurally determined organopalla-
dium(or -platinum) complexes are close to square planar
with the dihedral angle of 2.0–7.3ꢁ (Table 7).
As linked with these facts, the geometry of W for 17 had
four-leg piano-stool type structure, consisting of three car-
bonyl and Pt fragment, rather than three-leg piano-stool
type structure. This feature is indicated by larger dihedral
angle between Pt(1)–W(1)–C(30) and Pt(1)–W(1)–C(31)
planes for 17 (51.9ꢁ) than those for other structurally deter-

3706
N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
Table 7
complexes, being consistent with Pt(II)/W(0) formalism
rather than Pt(0)/W(II).
Dihedral angle between ML2 and MRM0 plane and dihedral angle
between MM0CO planes of organoplatinum(or -palladium)–molybde-
num(or -tungsten) complex
4. Experimental
L2RM–M0Cp(CO)3
Dihedral angle Dihedral angle
between ML2 between
and MRM0
MM0CO
4.1. General
plane (ꢁ)
planes (ꢁ)
All manipulations were carried out under dry nitrogen
or argon atmosphere using standard Schlenk and vacuum
line techniques [13]. Solvents were refluxed over and dis-
tilled from appropriate drying agents under N2: benzene,
toluene, hexane, THF and Et2O from sodium benzophe-
none ketyl; acetone from drierite; CH2Cl2 from P2O5. Deu-
terated solvents were degassed by three freeze–pump–thaw
cycles and then vacuum transferred from appropriate dry-
ing agents (C6D6 from sodium wire, acetone-d6 from drie-
rite). AgNO3 and CO (99.9%) were used as received. NMR
spectra were recorded on a JEOL LA-300 spectrometer
(cod)PhPt–MoCp(CO)3 (2)
(cod)PhPt–WCp(CO)3 (4)
(dppe)EtPt–MoCp(CO)3 (6)
(dppe)MePt–WCp(CO)3 (7)
(dppe)(EtCO)Pt–WCp(CO)3 (17)
(dppe)(Me3CH2CO)Pt–MoCp(CO)3 (18)
(Ph2PC2H4NEt2)PhPt–MoCp(CO)3 (19)
(tmeda)PhPt–MoCp(CO)3 (20)
(tmeda)PhPd–MoCp(CO)3 (12)
(bpy)PhPd–MoCp(CO)3 (13)
3.808
4.773
19.964
19.813
5.813, 3.051 27.597, 24.51
2.009
24.165
6.174
5.574
4.410
7.259
3.534
29.729
52.211
26.549
13.768
17.188
17.486
32.652
1
(300.4 MHz for H and 121.6 MHz for 31P) with chemical
Pt and W metals in 17 is considered to be caused essentially
by their steric constraint around the metal, rather than by
electronic influence of the ligands, and/or intermolecular
crystal packing effect. Conformation of the W (or Mo)
moiety may also be important. The Cp moiety locates close
to the acyl ligand in 17, but is placed in the phosphorus
ligand side in 18. Similar distortion from square planar
geometry at platinum has been observed for bis(germyl)-
[10], bis(stannyl)- [11], and bis(silyl)-platinum complexes
[11a,12] having monodentate phosphine ligands, where
the steric congestion is associated with the large substiu-
tents on the P, Ge, Sn and Si atoms. The most interesting
consequence is that twisting deformation from square pla-
nar around Pt in 17, which is intrinsically induced by the
steric constraint, caused the geometrical change of W moi-
ety from three-leg to four-leg piano-stool structure.
1
shifts reported in ppm downfield from TMS for H and
from 85% H3PO4 in D2O for 31P. IR spectra were recorded
on a JASCO FT/IR-410 spectrometer using KBr disk. Ele-
mental analyses were carried out with a Perkin–Elmer 2400
series II CHN analyzer. Molar electrical conductivity was
measured on a TOA Conduct Meter CM 7B.
The starting materials and related complexes were pre-
pared by the literature methods with modifications:
PdPhI(tmeda) [5a], PdPhI(bpy) [5b], Na[MoCp(CO)3] [6a],
and Na[WCp(CO)3] [6b] were prepared according to litera-
ture procedures. PdPhI(phen) was prepared by the reaction
of PdPhI(tmeda) with 1,10-phenathroline according to anal-
ogous literature method [5b]. Pt(CH2CMe3)Cl(dppe) was
prepared by the ligand substitution reaction of
Pd(CH2CMe3)Cl(cod) [14] with an equimolar amount of
dppe in CH2Cl2 at room temperature. The precipitated
white powder was washed with hexane, and recrystallization
from a mixture of CH2Cl2 and hexane gave white crystals.
3. Conclusion
In the present study, synthesis of novel heterodinuclear
phenylpalladium–molybdenum(or -tungsten) complexes
having a bidentate nitrogen ligand, L2PhPd–MCp(CO)3
(M = Mo, L2 = tmeda (12), bpy (13), phen (14); M = W,
L2 = tmeda (15)) by metathetical reactions of PdPhIL2
with Na[MCp(CO)3] is described. We also performed the
CO insertion of Pt–C bond in heterodinuclear alkylplati-
num–molybdenum(or -tungsten) complexes, giving novel
heterodinuclear acylplatinum–molybdenum(or -tungsten)
complexes, (dppe)(RCO)Pt–MCp(CO)3 (R = Et, M = Mo
(16), M = W (17); R = CH2CMe3, M = Mo (18)). The
geometry at Pt (or Pd) is square planar and the MCp(CO)3
moiety has three-leg piano-stool geometries in these com-
plex except the propionylplatinum–tungsten complex 17,
which shows apparent but unexpected structural deforma-
tion at Pt and W, giving twisted square-planar and four-leg
piano-stool geometries for formal platinum(0) and tung-
sten(II), respectively. However, similarity in reactivity of
17 and ethyl derivative 8 with methyl iodide suggests that
Pt is essentially electrophilic and W is nucleophilic in these
4.2. Synthesis of heterodinucler organopalladium complexes
having a bidentate nitrogen ligand
A typical procedure for (tmeda)PhPd–MoCp(CO)3 (12)
is given. To a THF solution of PdPhI(tmeda) (401.3 mg,
0.941 mmol) was added AgNO3 (242.4 mg, 1.43 mmol).
Stirring at room temperature for overnight gave a colorless
solution with a white precipitate of AgCl. To the filtered
solution, a THF solution of Na[MoCp(CO)3] (357.3 mg,
1.33 mmol) was added at ꢀ20 ꢁC and mixture stirred for
2 h. The resulting solution was evaporated to dryness and
resulting solid was extracted with benzene. After the fil-
tered solution was again evaporated to dryness, the yel-
low-brawn solids were solved with toluene and addition
of hexane gave orange cubic crystals, which were dried
under vacuum. Yield: 15% (76.3 mg, 0.140 mmol). M.p.
110 ꢁC (dec.). K (THF, r.t.) = 0.002 S cm2 molꢀ1. Anal.
Calc. for C20H26MoN2O3Pd: C, 44.09; H, 4.81; N, 5.14.
Found: C, 44.74; H, 4.71; N, 5.08%.

N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
3707
1H NMR and IR data of the new heterodinuclear phe-
nylpalladium complexes 12–15 are summarized in Table
1. Complex 13–15 were synthesized by a similar method
to that for 12.
tion with a precipitate of AgCl. To the filtered solution, a
THF solution of Na[MoCp(CO)3] (104.8 mg, 0.391 mmol)
was added at ꢀ50 ꢁC and mixture stirred for 3 h. The
resulting solution was evaporated to dryness and resulting
dark red solids extracted with benzene. After the filtered
solution was again evaporated to dryness, the crude prod-
uct (129.1 mg) was dissolved THF under N2 and the solu-
tion was degassed in a Schlenk tube. CO (1 atm) was
introduced into the Schlenk tube. After stirring for over-
night, the reaction mixture was evaporated to dryness in
vacuo giving brawn solid. Recrystallization from THF with
hexane gave orange prismatic crystal of 18 in 11% yield
(15.1 mg, 0.0161 mmol) from Pt(CH2CMe3)Cl(dppe). This
complex was identified by spectroscopic methods as well
(bpy)PhPd–MoCp(CO)3 (13). PdPhI(bpy) was used
instead of PdPhI(tmeda). This compound was obtained
dark red cubes from a mixture of CH2Cl2 and diethyl ether.
Yield: 46%. M.p. 162–163 ꢁC (dec.). K (THF, r.t.):
0.027 S cm2 molꢀ1. Anal. Calc. for C24H18MoN2O3Pd: C,
49.29; H, 3.10; N, 4.79. Found: C, 49.28; H, 2.63; N, 5.05%.
(phen)PhPd–MoCp(CO)3 (14). PdPhI(phen) was used
instead of PdPhI(tmeda). This compound was obtained
as red needles from acetone. Yield: 43%. M.p. 137 ꢁC
(dec.). K (THF, r.t.): 0.042 S cm2 molꢀ1. Anal. Calc. for
C24H18MoN2O3Pd: C, 51.29; H, 2.98; N, 4.60. Found: C,
51.45; H, 3.34; N, 4.49%.
(tmeda)PhPd–WCp(CO)3 (15). Na[WCp(CO)3] was
used instead of Na[MoCp(CO)3]. This compound was
obtained as dark red cubes from a mixture of CH2Cl2
and hexane. Yield: 18%. M.p. 162–163 ꢁC (dec.). K
(THF, r.t.): 0.013 S cm2 molꢀ1. Anal. Calc. for C20H26-
WN2O3Pd: C, 37.97; H, 4.14; N, 4.43. Found: C, 37.87;
H, 3.85; N, 4.28%.
1
as X-ray structure analysis. H and 31P{1H} NMR and
IR data of 18 are summarized in Table 2.
4.5. X-ray structure analyses
A Rigaku four-circle diffractometer with graphite-
˚
monochromatized Mo Ka radiation (0.71069 A) was used
for data collection. A single crystal was selected by use of
a polarized microscope and mounted in a capillary tube
(GLASS, 0.7 mmB), which was sealed by small flame
torch, or onto a glass capillary with Paraton N oil. The unit
cells were determined by the automatic indexing of the 20
centered reflections. The structures were solved and refined
using the texsan program system (Rigaku) [15]. The crystal-
lographic data and details associated with data collection
are given in Tables 3 and 4. ORTEP drawing is illustrated
in Figs. 1 and 2 and the bond lengths and bond angles are
listed in Tables 5 and 6.
Complex 7. The structure was solved by the direct meth-
ods (SAPI91) and refined by a full-matrix least-squares
procedure. All the non-hydrogen atoms except C(10),
C(12), C(13) and the incorporated solvent molecule were
refined anisotropically. All hydrogen atoms were included
in the calculation, but they were not refined.
Complex 12. The structure was solved by the Patterson
methods (DIRDIF 94 PATTY) and refined by a full-matrix
least-squares procedure. The methylene carbon atoms,
C(9), C(10), C(90), and C(100) of TMEDA have been found
disordered due to the k and d conformers. The two positions
were refined with occupancies of 58% and 42% with isotropic
displacement parameters. The other non-hydrogen atoms
except C(8) were refined anisotropically. All hydrogen
atoms expect methylene hydrogen atoms of tmeda ligand
were included in the calculation, but they were not refined.
Complex 13. The structure was solved by the Patterson
methods (DIRDIF 94 PATTY) and refined by a full-matrix
least-squares procedure. All the non-hydrogen atoms were
refined anisotropically. All hydrogen atoms were included
in the calculation, but they were not refined.
The dinuclear alkylplatinum complexes (dppe)RPt–
MCp(CO)3 (R = Me, M = Mo (5),
W (7); R = Et,
M = Mo (6), W (8)) were prepared according to the proce-
dures reported previously [3d,3e].
4.3. Synthesis of acyl complexes by CO insertion
A typical preparative procedure of (dppe)(EtCO)Pt–
MoCp(CO)3 (16) is given. 6 (146.8 mg, 0.1692 mmol) was
dissolved in toluene (15 ml) under N2 and the solution
was degassed in a Schlenk tube. CO (1 atm) was introduced
into the Schlenk tube. After stirring for a week, the reac-
tion mixture was evaporated to dryness in vacuo giving
brawn solid. Recrystallization from benzene/hexane gave
orange powders of 16 in 38% yield (58.1 mg, 0.0649 mmol).
M.p. 174 ꢁC (dec.). K (THF, r.t.): 0.14 S cm2 molꢀ1. Anal.
Calc. for C43H40O4PtMo: C, 50.82; H, 4.48. Found: C,
50.82; H, 4.48%.
1H and 31P{1H} NMR and IR data of the new heterodi-
nuclear acylplatinum complexes 16 and 17 are summarized
in Table 2. Complex 17 was synthesized by a similar
method to that for 16.
(dppe)(EtCO)Pt–WCp(CO)3 (17). This compound
was obtained as orange plates from benzene/hexane. Yield:
34%. M.p. 189 ꢁC (dec.). K (THF, r.t.): 0.084 S cm2 molꢀ1
.
Anal. Calc. for C43H40O4PtW: C, 45.18; H, 3.49. Found: C,
45.61; H, 3.60%.
4.4. Synthesis of (dppe)(Me3CCH2CO)Pt–MoCp(CO)3
(18)
Complex 17. The structure was solved by the direct
methods (SAPI91) and refined by a full-matrix least-
squares procedure. All the non-hydrogen atoms except the
incorporated solvent molecule were refined anisotropically.
To a solution of Pt(CH2CMe3)Cl(dppe) (99.4 mg,
0.142 mmol) was added AgNO3 (38.3 mg, 0.226 mmol).
Stirring at room temperature for 1 h gave a colorless solu-

3708
N. Komine et al. / Inorganica Chimica Acta 359 (2006) 3699–3708
(i) N. Komine, H. Hoh, M. Hirano, S. Komiya, Organometallics 19
(2000) 5251;
(j) A. Fukuoka, S. Fukagawa, M. Hirano, N. Koga, S. Komiya,
Organometallics 20 (2001) 2065;
(k) S. Tsutsuminai, N. Komine, M. Hirano, S. Komiya, Organomet-
allics 22 (2003) 4238;
(l) S. Tsutsuminai, N. Komine, M. Hirano, S. Komiya, Organomet-
allics 23 (2004) 44.
All hydrogen atoms were included in the calculation, but
they were not refined.
Complex 18. The structure was solved by the Patterson
methods (DIRDIF 94 PATTY) and refined by a full-matrix
least-squares procedure. All the non-hydrogen atoms
except C(6) and the incorporated solvent molecule were
refined anisotropically. All hydrogen atoms were included
in the calculation, but they were not refined.
Complex 20. The structure was solved by the direct
methods and refined by a full-matrix least-squares proce-
dure. The methylene carbon atoms, C(9), C(10), C(90),
and C(100) of TMEDA have been found disordered due
to the k and d conformers. The two positions were refined
with occupancies of 53% and 47% with isotropic displace-
ment parameters. The other non-hydrogen atoms except
C(8) were refined anisotropically. All hydrogen atoms
expect methylene hydrogen atoms of tmeda ligand were
included in the calculation, but they were not refined.
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The work was financially supported by Grant-in-Aid for
Scientific Research from the Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan and the 21th
Century COE Program of ‘‘Future Nano-materials’’ in
Tokyo University of Agriculture and Technology.
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