Synthesis, structure and reactivities of novel σ-ruthenocenylplatinum complexes

Article abstract of DOI:10.1016/S0022-328X(98)00972-3

Novel σ-ruthenocenylplatinum complexes (3) and (4) have been synthesized by the reaction of trimethylstannylruthenocene (1) or 1,1′-bis(trimethylstannyl)ruthenocene (2) with Pt(cod)Cl₂, and characterized by means of spectral analyses as well we

Full text of DOI:10.1016/S0022-328X(98)00972-3

Journal of Organometallic Chemistry 574 (1999) 66–76
Synthesis, structure and reactivities of novel |-ruthenocenylplatinum
complexesꢀ
Toshiya Yoshida a, Takahiro Shinohara a, Kiyotaka Onitsuka a,*, Fumiyuki Ozawa a,1
Kenkichi Sonogashira b,2
,
a Department of Applied Chemistry, Faculty of Engineering, Osaka City Uni6ersity, Sumiyoshi-ku, Osaka 558-0022, Japan
b Department of Applied Science and Chemistry, Faculty of Engineering, Fukui Uni6ersity of Technology, 3-6-1 Gakuen, Fukui 910-8505, Japan
Received 8 June 1998
Abstract
Novel |-ruthenocenylplatinum complexes (3) and (4) have been synthesized by the reaction of trimethylstannylruthenocene (1)
or 1,1%-bis(trimethylstannyl)ruthenocene (2) with Pt(cod)Cl2, and characterized by means of spectral analyses as well we an X-ray
diffraction study. In the cyclic voltammogram of complexes 3 and 4, irreversible two successive one-electron oxidation peaks of
the ruthenocenyl group appear at lower potential than that of irreversible single-step two electron oxidation of ruthenocene. The
treatments of |-ruthenocenylplatinum complex (5) with carbon monoxide and aryl isocyanides cause the insertion into Pt–C bond
to give insertion products (7) and (9), respectively. The reaction of 5 with dimethyl or diethyl acetylenedicarboxylate results in the
formal insertion of acetylene into the C–H bond of the cyclopentadienyl group at 2-position to give 11 as observed in the reaction
of |-ferrocenyl analog (6). Competitive reactions of complexes 5 and 6 with CO, isocyanide or acetylene suggest that the reactivity
of 5 towards these substrates is not as high as that of 6. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Platinum complex; Ruthenocene; Insertion; Carbon monoxide; Isocyanide; Acetylene
1. Introduction
shows an irreversible one-step two electron oxidation at
a higher potential than that of ferrocene [4].
Ferrocene, which is one of the representative organo-
metallic compounds, has been of particular interest ever
since its discovery in 1951 because of its unique struc-
ture and properties applicable to wide scientific fields
[1]. Ruthenocene is a ferrocene analog of ruthenium,
and has a typical sandwich structure with larger separa-
tion between two cyclopentadienyl rings relative than
that of ferrocene [2,3]. In contrast to a reversible one
electron redox behavior of ferrocene, ruthenocene
Recently metallocenyl transition-metal complexes
have been received much attention since some of which
show an intramolecular interaction between transition-
metal atom and a central metal atom of metallocenyl
ligand [5]. In the course of our study on |-ferro-
cenylplatinum complexes, we have found that a ferro-
cenyl group acts as an electron pool controlling the
reactivity of a platinum center [6]. Thus, |-ferro-
cenylplatinum complexes show characteristic reactivi-
ties with CO, isocyanide and acetylene [7,8]. The
remarkable feature of ruthenocene has led us to the
chemistry of |-ruthenocenylplatinum complexes, which
may show the different or specific reactivity with rela-
tive to that of |-ferrocenyl analog owing to the elec-
tronic and/or structural feature of the ruthenocenyl
ligand. In comparison with many publications on |-fer-
ꢀ Dedicated to the late Professor Rokuro Okawara on the occasion
of his memorial issue.
* Corresponding author. Present address: Institute of Scientific and
Industrial Research, Osaka University, Ibaraki, Osaka 567-0047,
Japan.
1 Also corresponding author.
2 Also corresponding author.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)00972-3

T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
67
rocenyl transition-metal complexes, a limited number of
studies on |-ruthenocenyl transition-metal complexes
have appeared in the literature [9]. Thus, we present
here the synthesis of novel |-ruthenocenylplatinum
complexes and their reactivity of Pt–C bond toward
insertion of CO, isocyanide and acetylene.
2. Results and discussion
2.1. Syntheses of |-ruthenocenylplatinum complexes
Fig. 1. Cyclic voltammogram of 3 (1.9×10−3 M in CH2Cl2); scan
rate 100 mV s−1, supporting electrolyte Bu4NPF6 (1.0×10−1 M),
working electrode Pt-disk (2 mm diameter).
As a synthetic strategy of |-ruthenocenylplatinum
complexes, transmetallation of trimethylstannylruthe-
nocene with Pt(cod)Cl2, that is a similar method used
for the synthesis of |-ferrocenylplatinum complex [10],
was chosen. Treatment of ruthenocene with excess n-
BuLi (ca. 2.4 equivalents) in THF at −50°C followed
by treatment with trimethylstannylchloride at 0°C gave
a mixture of ruthenocene, trimethylstannylruthenocene
(1) and 1,1%-bis(trimethylstannyl)ruthenocene (2) in a
1:6:3 molar ratio (determined by GLC analysis). Since
we could not isolate complexes 1 and 2, this mixture
was treated with Pt(cod)Cl2 in refluxing THF and the
resulting products were separated by column chro-
matography on alumina. RcPt(cod)Cl (Rc=
(C5H4)Ru(C5H5)) (3) and {C5H4Pt(cod)Cl}2Ru (4) were
obtained from benzene fraction in 64% yield and from
CH2Cl2 fraction in 37% yield, respectively. These com-
plexes 3 and 4 are air and moisture stable at ambient
temperature both in the solid state and in solution.
Characterization of these complexes was made by the
1H- and 13C-NMR spectra as well as an X-ray analysis
(Scheme 1).
tron density of the cyclopentadienyl rings in the
ruthenocenyl compounds relative to ferrocenyl analogs
[12]. Similar shifts of the signals attributed to substi-
tuted cyclopentadienyl protons into lower magnetic
1
field was also observed in the H-NMR spectrum of 4.
Subsequently, the electrochemical properties of 3 and
4 were studied by cyclic voltammetry. In contrast to a
reversible one-electron redox behavior of the ferrocenyl
group in FcPt(cod)Cl [11], the cyclic voltammogram of
3 (Fig. 1) exhibited irreversible two successive one-elec-
tron oxidation peaks of the ruthenocenyl moiety Ea=
0.53 V (RuII/RuIII); 0.80 V (RuIII/RuIV) relative to
Ag/AgCl at the Pt-disc electrode in dichloromethane
solution. If one considers that ruthenocene undergoes
an irreversible single-step two electron oxidation at
Ea=0.88 V, it appears that the platinum fragment
strongly donates electron density to the ruthenocenyl
group and stabilizes the ruthenocenium cation fragment
[11,13]. Complex 4 also showed similar oxidation be-
havior at lower potential Ea=0.35 V (RuII/RuIII); 0.58
V (RuIII/RuIV) relative to Ag/AgCl in the cyclic voltam-
mogram as shown in Fig. 2. The shift of oxidation
potential of 4 relative to 3 is also explained by the
strong electron donation of the platinum moieties.
The molecular structure of 3 is shown in Fig. 3 and
selected bond lengths and angles are given in Table 1.
The environment of the Pt atom is the expected square-
planar with |-bond to the ruthenocenyl group and
The 1H-NMR spectrum of 3 showed two triplet
signals at l 5.60 and 5.11 attendant with 195Pt satellite
peaks (2JPt–H=29.3 and 74.7 Hz, respectively) at-
tributed to olefinic protons of a cod ligand, along with
two triplets of substituted cyclopentadienyl protons at l
4.69 and 4.60, and a singlet of non-substituted cy-
clopentadienyl protons at l 4.59. The resonances of
cyclopentadienyl protons of 3 appeared much lower
field than those of |-ferrocenyl analogs, FcPt(cod)Cl
(Fc=(C5H4)Fe(C5H5)) [11], suggesting the lower elec-
Fig. 2. Cyclic voltammogram of 4 (1.0×10−3 M in CH2Cl2); scan
rate 100 mV s−1, supporting electrolyte Bu4NPF6 (1.0×10−1 M),
working electrode Pt-disk (2 mm diameter).
Scheme 1.

68
T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
Fig. 3. Molecular structure of 3. Hydrogen atoms have been omitted for clarity.
y-bonds to the cyclooctadiene ligand. The Pt(1)–C(1)
bond length trans to cyclooctadiene is 2.033(5) A,
essentially parallel and the ruthenocenyl group has an
eclipsed conformation.
˚
which is comparable to those observed in Pt(-
cod){Fe(C5H4Cl)(C5H3Cl)}2 (2.003(19) and 2.042(16)
The molecular structure of 4 is also illustrated in Fig.
4 and selected bond lengths and angles are listed in
1
Table 2. As expected from H- and 13C-NMR spectra,
˚
˚
A) [14] and {C5H4Pt(cod)Cl}Mn(CO)3 (2.04(1) A) [15].
The Pt(1)–C(11) and Pt(1)–C(12) bond lengths
two platinum atoms are |-bonded to both cyclopenta-
dienyl rings and the coordination around the each
platinum atom is similar to that of 3. It may be of
interest that two bulky platinum moieties are closely
located each other by the rotation of cyclopentadienyl
groups. However, the distance between Pt(1) and Pt(2)
˚
(2.284(6) and 2.315(5) A) are longer than those of
˚
Pt(1)–C(15) and Pt(1)–C(16) (2.126(6) and 2.155(5) A),
˚
and the bond distance of C(11)–C(12) (1.367(8) A) is
˚
shorter than that of C(15)–C(16) (1.392(8) A). These
phenomena are due to the difference of trans influence
between the ruthenocenyl group and the Cl ligand. The
dihedral angle between the plane containing Pt(1), C(1)
and Cl(1), and the cyclopentadienyl ring consisting of
C(1)–C(5) is 14.6°. The two cyclopentadienyl rings are
˚
is 4.5983(9) A, suggesting no direct interaction between
two platinum atoms. The distances of Pt(1)–Cl(2) and
˚
Pt(2)–Cl(1) are \4 A, which are clearly in the range of
nonbonding distances. Therefore, the conformation of
cyclopentadienyl groups bound to a platinum moiety is
likely due to crystal-packing force.
Table 1
Complex 3 was easily converted to a phosphine
analog 5 by a ligand-exchange reaction. Thus, treat-
ment of 3 with triethylphosphine gave complex 5a in
85% yield. Treatment of 5a with excess NaBr or
NaSCN in methanol caused an exchange of an anion
ligand to give 5b and 5c, respectively. Since slow evapo-
ration of hexane solution of 5c gave fine crystals, an
X-ray analysis was performed. There are two indepen-
dent molecules with essentially the same structure in a
unit cell. One of the two molecular structures of 5c is
shown in Fig. 5 and selected bond lengths and angles
are listed in Table 3. Pt–C bond lengths are 2.032(8)
˚
Selected bond lengths (A) and angles (°) for 3
˚
Bond lengths (A)
Pt(1)–C(1)
Pt(1)–C(11)
Pt(1)–C(12)
Pt(1)–C(15)
2.033(5) Pt(1)–C(16)
2.284(6) Pt(1)–Cl(1)
2.315(5) C(11)–C(12)
2.126(6) C(15)–C(16)
2.155(5)
2.319(2)
1.367(8)
1.392(8)
Bond angles (°)
Cl(1)–Pt(1)–C(1)
Cl(1)–Pt(1)–C(11)
Cl(1)–Pt(1)–C(12)
C(1)–Pt(1)–C(15)
C(1)–Pt(1)–C(16)
91.2(2)
86.9(2)
92.4(2)
91.3(2)
95.0(2)
C(11)–Pt(1)–C(16)
95.7(2)
34.6(2)
80.4(2)
37.9(2)
C(11)–Pt(1)–C(12)
C(12)–Pt(1)–C(15)
C(15)–Pt(1)–C(16)

T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
69
Fig. 4. Molecular structure of 4. Hydrogen atoms have been omitted for clarity.
˚
and 2.030(8) A, respectively. These values are compara-
atoms make dihedral angles with the cyclopentadienyl
planes of 80.3 and 81.7°, respectively.
ble those of |-ruthenocenylplatinum complexes (vide
supra). Since a bulky platinum group is directly linked
to the cyclopentadienyl group, the ruthenocenyl moiety
has a strained structure with the tilt angle between two
cyclopentadienyl planes of 10.1 and 9.3°, respectively
[8]. The platinum atoms lie at a distance of 0.61 or 0.63
A from the plane of the bound cyclopentadienyl group,
which is also due to the steric effect of the bulky
platinum moiety. The coordination planes around Pt
2.2. Reaction of carbon monoxide, aryl isocyanide and
acetylene with |-ruthenocenylplatinum complexes
In analogy with |-ferrocenylplatinum complexes (6),
reactions of |-ruthenocenylplatinum complexes 5 with
CO, aryl isocyanide and acetylene having an electron-
withdrawing group were investigated (Scheme 2). When
complex 5a was treated with 30 kg cm−2 of CO at
room temperature (r.t.) for 24 h pale yellow crystals of
trans-RcC(O)Pt(PEt3)2Cl (7a) were obtained in 88%
yield. The IR and 13C-NMR spectra indicated that 7a
was produced by insertion of CO into the Pt–C bond
of 5a. The CO stretching vibration was observed at
1610 cm−1 in the IR spectrum of 7a. The resonance
attributed to carbonyl carbon appeared at l 211.6 in
the 13C-NMR spectrum [7]. It is noteworthy that the
insertion of CO into the Pt–C bond occurs at r.t. as
observed |-ferrocenyl platinum analogs 6 though the
˚
Table 2
˚
Selected bond lengths (A) and angles (°) for 4
˚
Bond lengths (A)
Pt(1)–C(1)
Pt(1)–C(11)
Pt(1)–C(12)
Pt(1)–C(15)
Pt(1)–C(16)
Pt(1)–Cl(1)
C(11)–C(12)
C(15)–C(16)
2.031(9) Pt(2)–C(6)
2.030(9)
2.12(1)
2.14(1)
2.26(1)
2.27(1)
2.317(3)
1.39(2)
1.37(2)
2.13(1)
2.16(1)
2.27(1)
2.28(1)
Pt(2)–C(19)
Pt(2)–C(20)
Pt(2)–C(23)
Pt(2)–C(24)
2.342(3) Pt(2)–Cl(2)
1.38(1)
1.36(2)
C(19)–C(20)
C(23)–C(24)
Bond angles (°)
Cl(1)–Pt(1)–C(1)
Cl(1)–Pt(1)–C(15)
Cl(1)–Pt(1)–C(16)
C(1)–Pt(1)–C(11)
C(1)–Pt(1)–C(12)
C(11)–Pt(1)–C(16) 81.2(4)
C(15)–Pt(1)–C(16) 34.8(4)
C(12)–Pt(1)–C(15) 81.7(5)
C(11)–Pt(1)–C(12) 37.7(4)
carbonylation of trans-RPt(PR%) X was achieved at
3 2
91.1(3)
87.7(4)
92.4(2)
92.6(4)
93.4(4)
Cl(2)–Pt(2)–C(6)
Cl(2)–Pt(2)–C(23)
Cl(2)–Pt(2)–C(24)
C(6)–Pt(2)–C(19)
C(6)–Pt(2)–C(20)
C(19)–Pt(2)–C(24)
C(19)–Pt(2)–C(20)
C(20)–Pt(2)–C(23)
C(23)–Pt(2)–C(24)
91.9(3)
90.4(4)
88.2(4)
93.1(4)
91.3(4)
80.9(5)
38.0(5)
81.6(5)
35.1(5)
90°C [16]. The similar treatment of 5b gave the inser-
tion product, trans-RcC(O)Pt(PEt3)2Br (7b), in 88%
yield, but the reaction of 5c with CO afforded the
acylplatinum complex 7c in only 11% yield.
On treatment of 5a with 1.2 equivalent of p-tolyliso-
cyanide in refluxing 1,2-dichloroethane for 6 h, a yellow
complex, trans-RcC(ꢀNC6H4Me-p)Pt(PEt3)2Cl (9a),
which is resulted from insertion of isocyanide into the

70
T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
Fig. 5. Molecular structure of 5c. Hydrogen atoms have been omitted for clarity.
Pt–C bond of 5a, was isolated in 63% yield. The
insertion of isocyanide is revealed by the w(CꢀN) ab-
sorption at 1550 cm−1 in the IR spectrum of 9a and the
resonance of iminoacyl carbon at l 172.1 in the 13C-
NMR spectrum [7]. 31P-NMR spectrum of 9a showed a
singlet signal at l 14.70 with satellite signals due to the
coupling of 195Pt nucleus (JPt–P=2894 Hz), indicating
manner also afforded the insertion product, trans-
RcC(ꢀNC6H3Me2-2,6)Pt(PEt3)2Cl (9b) or trans-
RcC(ꢀNC6H4NO2-p)Pt(PEt3)2Cl (9c), in 36 and 50%
yields, respectively.
The molecular structure of 9a is shown in Fig. 6.
p-Tolyl isocyanide is undoubtedly inserted into the
Pt–C bond of 5a to form iminoacylplatinum complex
and the coordination sphere around the Pt atom is a
1
the trans conformation around the Pt atom. H-NMR
spectrum and the results of elemental analysis were also
consistent with the structure of 9a. The reaction of 5a
with 2,6-xylyl or p-nitrophenyl isocyanide in a similar
Table 3
˚
Selected bond lengths (A) and angles (°) for 5c
˚
Bond lengths (A)
Pt(1)–P(1)
Pt(1)–P(2)
Pt(1)–N(1)
Pt(1)–C(1)
2.293(3) Pt(2)–P(3)
2.329(3) Pt(2)–P(4)
2.039(7) Pt(2)–N(2)
2.032(8) Pt(2)–C(31)
2.296(2)
2.317(3)
2.070(8)
2.030(8)
Bond angles (°)
P(1)–Pt(1)–P(2)
P(1)–Pt(1)–N(1)
P(1)–Pt(1)–C(1)
P(2)–Pt(1)–N(1)
P(2)–Pt(1)–C(1)
176.17(9)
P(3)–Pt(2)–P(4)
P(3)–Pt(2)–N(2)
P(3)–Pt(2)–C(31)
P(4)–Pt(2)–N(1)
P(4)–Pt(2)–C(31)
N(2)–Pt(2)–C(31)
175.36(9)
89.2(2)
94.6(2)
87.9(2)
88.2(2)
175.8(3)
89.3(2)
94.9(2)
87.9(2)
87.8(2)
N(1)–Pt(1)–C(1) 175.7(3)
Scheme 2.

T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
71
Fig. 6. Molecular structure of 9a · CHCl3. Hydrogen atoms and a solvent molecule have been omitted for clarity.
square-planar with two PEt3 ligands in mutually trans
[7]. The tilt angle between two cyclopentadienyl rings of
positions. Table 4 lists selected bond lengths and angles.
The Pt(1)–C(11) bond length of 2.03(2) A is compara-
ble with those of other trans-iminoacylplatinum com-
the moiety ruthenocene is 0.8°.
˚
Complex 5a was treated with slight excess of
dimethylacetylenedicarboxylate (DMAD) in benzene at
reflux temperature for 24 h and the yellow crystals of
11a was obtained in 25% yield. The IR spectrum of 11a
showed a w(CꢀC) absorption at 1610 cm−1 and two
plexes [17]. The Pt(1)–Cl(1) bond distance is 2.438(5)
˚
A, which is longer than those of 3 and 4 (vide supra)
and comparable to that of trans-FcC(O)Pt(PEt3)2Cl (8)
(2.441(2) A) [7], indicating the strong trans influence of
w(CꢀO) absorptions at 1735 and 1705 cm−1. The H-
1
˚
the iminoacyl group as well as an acyl group. The plane
of the iminoacyl group defined by Pt(1), C(11), C(1),
N(1) and C(12) makes dihedral angles with the Pt
coordination plane and the cyclopentadienyl ring C(1)–
C(5) for 72.8 and 31.1°, respectively. The former is
smaller than that of a ferrocenyl analog (10) having a
cis geometry, while the latter is larger than that of 10
NMR spectrum exhibited a signal of the olefinic proton
at l 7.94 and three resonances of the substituted cy-
clopentadienyl ring protons at l 4.67, 4.63 and 4.52. All
1
of the spectroscopic data (IR, H-, 13C- and 31P-NMR)
for 11a are similar to those of a ferrocenyl analog (12a)
(X=Cl; R=CO2Me) [8], indicating that 11a has a
similar structure to that of 12a, i.e. 11a was produced
by the formal insertion of DMAD into the C–H bond
at 2-position of the ruthenocenyl group. Similar treat-
ments of 5b with DMAD and 5a with diethyl
acetylenedicarboxylate afforded 11b in 40% yield and
11c in 30% yield, respectively. The reaction mechanism
of the formation of 11 will be identical with that of 12
as previously reported.
Table 4
˚
Selected bond lengths (A) and angles (°) for 9a · CHCl3
˚
Bond lengths (A)
Pt(1)–Cl(1)
Pt(1)–P(1)
Pt(1)–P(2)
Pt(1)–C(11)
2.438(5) C(1)–C(11)
2.320(6) N(1)–C(11)
2.299(6) N(1)–C(12)
2.03(2)
1.50(3)
1.230(2)
1.43(2)
Bond angles (°)
Cl(1)–Pt(1)–P(1)
Cl(1)–Pt(1)–P(2)
Cl(1)–Pt(1)–C(11)
P(1)–Pt(1)–P(2)
P(1)–Pt(1)–C(11)
90.1(2)
87.3(2)
177.7(6)
177.3(2)
90.2(6)
P(2)–Pt(1)–C(11)
92.4(6)
115(1)
127(2)
117(1)
124(2)
Pt(1)–C(11)–C(1)
Pt(1)–C(11)–N(1)
N(1)–C(11)–C(1)
C(11)–N(1)–C(12)

72
T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
Table 5
Crystallographic data for 3, 4, 5c and 9a·CHCl3
3
4
5c
9a·CHCl3
Formula
MW
C18H21ClPtRu
568.98
C26H32Cl2Pt2Ru
906.69
C23H39NP2PtRuS
719.74
C31H47Cl4NP2PtRu
933.64
Color, habit
Crystal size (mm)
Crystal system
Lattice parameters
Yellow, prismatic
0.35×0.25×0.25
Monoclinic
Colorless, needle
0.25×0.07×0.02
Monoclinic
Pale yellow, plate
0.25×0.25×0.10
Triclinic
Yellow, prismatic
0.30×0.20×0.10
Monoclinic
˚
˚
˚
˚
a=10.719(2) A
a=12.515(2) A
a=17.236(3) A
a=16.548(4) A
˚
˚
˚
˚
b=10.834(2) A
b=10.170(2) A
b=20.631(5) A
b=13.128(3) A
˚
˚
˚
˚
c=14.342(2) A
c=18.961(2) A
c=7.734(2) A
c=17.010(4) A
h=99.63(2)°
i=94.58(2)°
k=86.18(2)°
i=102.47(1)°
i=93.70(1)°
i=96.62(2)°
3
3
3
3
˚
˚
˚
˚
V=1626.3(3) A
V=2408.2(6) A
V=2705(1) A
V=3670(1) A
Space group
P21/n (no. 14)
4
2.324
97.52
6B2qB55.1
3956
P21/c (no. 14)
4
2.501
125.58
6B2qB50.1
4531
P1(no. 2)
4
1.767
59.70
6B2qB50.1
9920
P21/n (no. 14)
4
1.689
46.52
6B2qB50.2
7065
Z
Dcalc. (g cm−3
)
v(Mo–Kah) (cm−1
2q range (°)
)
No. of reflections measured
No. of observed reflections
No. of variables
2979 (I\3.0|(I))
190
3136 (I\3.0|(I))
280
6718 (I\3.0|(I))
523
2807 (I\2.0|(I))
361
Residuals: R; Rw
Goodness-of-fit
Max; min (D/z) (e A
0.026; 0.029
1.59
0.95; −2.32
0.032; 0.036
1.38
1.09; −0.92
0.036; 0.035
1.39
1.49; −1.29
0.064; 0.056
1.25
0.87; −1.47
−3
˚
)
cenyl groups are a strong electron-donating group,
electron density of the cyclopentadienyl ring of fer-
rocene is higher than that of ruthenocene as suggested
1
by the H-NMR spectra of 5a and 6a (vide supra) [12].
Therefore, the lower electron-donating feature of a
ruthenocenyl group than that of a ferrocenyl group
may causes the difference in the reactivity between
|-ruthenocenyl- and |-ferrocenylplatinum complexes.
The result that the carbonylation of {C5H4Pt(cod)
Cl}Mn(CO)3 requires heating at 100°C is consistent
with this explanation [15].
As shown above, reaction of |-ruthenocenylplatinum
complexes 5 with CO, aryl isocyanide and acetylene
having an electron-withdrawing group under the same
conditions for |-ferrocenylplatinum analog 6 gave sim-
ilar insertion products 7, 9 and 11, respectively. Conse-
quently, reactivity of |-ruthenocenylplatinum complex
5 toward insertion reactions was compared with those
of |-ferrocenylplatinum analog 6. A competitive reac-
tion of complexes 5a and 6a (X=Cl) with atmospheric
pressure of CO at r.t. (about 20°C) in benzene giving
acylplatinum complexes, 7a and 8a (X=Cl), was moni-
tored by 31P-NMR spectroscopy. The carbonylation of
6a is ca. 11 times faster than that of 5a. Similarly, the
insertion of p-nitrophenyl isocyanide into the Pt–C
bond of 6a is about 300 times faster than that of 5a at
r.t. in 1,2-dichloroethane. The rate of the reaction of 6a
with DMAD was also is ca. 2.5 times faster than that of
5a. These results indicate that reactivity of |-rutheno-
cenylplatinum complex 5a toward CO, isocyanide and
acetylene insertions is lower than that of |-ferro-
cenylplatinum analog 6. A study on the mechanism of
CO insertion into a Pt–C bond has shown that an
electron-donating substituent of an organic group en-
hances the rate of CO insertion [18]. Although metallo-
3. Experimental
All reactions except for the reaction with carbon
monoxide were performed under a nitrogen atmo-
sphere, and the workup was carried out in air. 1H-, 13C-
and 31P-NMR spectra were measured on a JEOL h400
1
spectrometer. For H and 13C-NMR SiMe4 was used as
an internal standard, and 31P-NMR spectra were re-
ferred to an external standard of PPh3. IR spectra were
recorded on a JASCO A-202 spectrometer. Cyclic
voltammetric measurement was performed in CH2Cl2 at
r.t. with 0.1 M tetrabutylammonium hexafluorophos-
phate as supporting electrolyte and the scan rate was
100 mV s−1. The reference electrode was Ag/AgCl
(acetonitrile) and working electrode was a platinum-
disc electrode (2 mm diameter). All chemicals were used
as received and aryl isocyanide were prepared accord-
ing to the literature method [19].

T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
73
3.1. Preparation of trimethylstannylruthenocene (1) and
1,1%-bis(trimethystannyl)ruthenocene (2)
low precipitate of 4 (308 mg) was obtained in 37% yield
by addition of hexane.
1
3: M.p. 163–167°C (dec.). H-NMR (CDCl3): l 5.60
A 1.6 M solution of n-BuLi in hexane (10.0 ml, 16.0
(t, J=2.6 Hz, 2JPt–H=29.3 Hz, 2H, ꢀCH), 5.11 (t,
2
mmol) was added dropwise to
a
solution of
J=2.6 Hz, JPt–H=74.7 Hz, 2H, ꢀCH), 4.69 (t, J=1.8
ruthenocene (1.516 g, 6.555 mmol) in THF (50 ml) at
−50°C. After stirring for 1 h at −50°C, the reaction
mixture was allowed to warm slowly to r.t. and stirred
for an additional 20 h. Then to a reaction mixture was
added dropwise a solution of Me3SnCl (2.710 g, 13.60
mmol) in THF (40 ml) at 0°C. After the addition was
complete, the mixture was allowed to warm at r.t. and
further stirred for 22 h. The solvent was removed under
vacuum and the resulting orange oil was dissolved in
benzene (50 ml) and washed three times with water (200
ml). The organic layer was separated, dried over
Na2SO4 and the benzene was evaporated under reduced
pressure. The residue was dissolved in hexane (50 ml)
again and filtered. Finally the filtrate was evaporated to
dryness in vacuo and the 1.712 g of mixture of
ruthenocene (10%), trimethylstannylruthenocene (1)
(60%) and 1,1%-bis(trimethystannyl)ruthenocene (2)
(30%) was obtained. This mixture was used for reaction
without further purification.
Hz, JPt–H=15.6 Hz, 2H, C5H4), 4.60 (t, J=1.8 Hz,
2H, C5H4), 4.59 (s, 5H, C5H5), 2.23–2.61 (m, 8H, CH2).
1
13C-NMR (CDCl3): l 112.0 (s, JPt–C=44.7 Hz, ꢀCH),
86.68 (s, 1JPt–C=205 Hz, ꢀCH), 80.94 (s, ipso C of
C5H4), 73.58 (s, JPt–C=39.7 Hz, C5H4), 71.23 (s, JPt–
C=44.7 Hz, C5H4), 70.16 (s, C5H5), 28.52 (s, CH2). CV
(in CH2Cl2, V vs. Ag/Ag+): Ea 0.53, 0.80. Anal. Found;
C, 38.12; H, 3.46; Cl, 6.50%. Calc. for C18H21ClPtRu:
C, 38.00; H, 3.72; Cl, 6.23%.
1
4: M.p. 191–197°C (dec.). H-NMR (CDCl3): l 5.58
(t, J=2.7 Hz, 2JPt–H=24.4 Hz, 4H, ꢀCH), 5.17 (t,
2
J=2.7 Hz, JPt–H=76.1 Hz, 4H, ꢀCH), 4.76 (t, J=1.6
Hz, 4H, C5H4), 4.62 (t, J=1.6 Hz, 4H, C5H4), 2.25–
2.65 (m, 16H, CH2). 13C-NMR (CDCl3): l 111.9 (s,
1JPt–C=44.7 Hz, ꢀCH), 86.69 (s, 1JPt–C=208 Hz,
ꢀCH), 81.57 (s, ipso C of C5H4), 73.76 (s, JPt–C=38.1
Hz, C5H4), 71.44 (s, JPt–C=39.7 Hz, C5H4), 28.51 (s,
CH2). CV (in CH2Cl2, V vs. Ag/Ag+): Ea 0.35, 0.58.
Anal. Found; C, 34.25; H, 3.33; Cl, 7.77%. Calc. for
C26H32Cl2Pt2Ru: C, 34.44; H, 3.56; Cl, 7.82%.
1
1: Yellow oil. H-NMR (CDCl3): l 4.69 (t, J=1.5
Hz, 2H, C5H4), 4.50 (s, 5H, C5H5), 4.41 (t, J=1.5 Hz,
2
2H, C5H4), 0.18 (s, JSn–H=53.2, 56.1 Hz, 9H, Me).
3.3. Preparation of trans-RcPt(PEt3)2Cl (5a)
13C-NMR (CDCl3): l 111.0 (s, ipso C of C5H4), 75.68
(s, JPt–C=51.3 Hz, C5H4), 72.26 (s, JPt–C=36.4 Hz,
C5H4), 69.94 (s, C5H5), −8.41 (s, JSn–C=361, 346 Hz,
To a solution of RcPt(cod)Cl (3) (102 mg, 0.179
mmol) in CH2Cl2 (30 ml) was added a 1.0 M solution
of PEt3 in THF (0.36 ml, 0.36 mmol) and the mixture
was stirred for 2 h at r.t. After removal of the solvent
in vacuo, the residue recrystallized from hexane gave
pale yellow crystals (106 mg, yield 85%). M.p. 107–
108°C. 1H-NMR(CDCl3): l 4.46 (t, J=1.5 Hz, 2H,
1
Me).
1
2: Yellow oil. H-NMR (CDCl3): l 4.62 (t, J=1.5
Hz, 4H, C5H4), 4.39 (t, J=1.5 Hz, 4H, C5H4), 0.18 (s,
2JSn–H=53.2, 55.6 Hz, 18H, Me). 13C-NMR (CDCl3):
l 75.49 (s, JPt–C=51.3 Hz, C5H4), 72.24 (s, JPt–C=36.4
1
Hz, C5H4), −8.41 (s, JSn–C=361, 344 Hz, Me). The
C5H4), 4.34 (s, 5H, C5H5), 4.27 (t, J=1.5 Hz, JPt–H=
resonance attributed to the C5H4 ipso carbons was not
detected.
28.3 Hz, 2H, C5H4), 1.97–1.89 (m, 12H, CH2), 1.10
(quintet, J=7.8 Hz, 18H, CH3). 13C-NMR (CDCl3): l
85.74 (t, 2JP–C=8.3 Hz, ipso C of C5H4), 78.07 (s,
3.2. Preparation of RcPt(cod)Cl (3) and {p5-C5H4Pt-
(cod)Cl}2Ru (4)
JPt–C=72.8 Hz, C5H4), 71.09 (s, C5H5), 67.75 (s, JPt–C
=61.2 Hz, C5H4), 12.40 (t, J=16.5 Hz, CH2), 7.93 (s,
1
CH3). 31P-NMR (CDCl3): l 22.15 (s, JPt–P=2714 Hz).
A 1.712 g of the mixture of ruthenocene (10%),
trimethylstannylruthenocene (1) (60%) and 1,1%-
bis(trimethystannyl)ruthenocene (1) (30%) was treated
with Pt(cod)Cl2 (1.614 g, 4.313 mmol) in THF (100 ml)
under reflux for 4 h. The solvent was distilled off under
reduced pressure and the residue was chromatographed
over alumina. Elution with benzene gave the following
bands in the order of elution: the pale yellow band of
ruthenocene (145 mg, 85% recovery) and the yellow
band of 3. The solvent was removed from the second
band in vacuo followed by recrystallization from
CH2Cl2/hexane to give yellow crystals of 3 (955 mg) in
64% yield. CH2Cl2 fraction was concentrated to dryness
and the residue was dissolved in CH2Cl2/benzene. Yel-
Anal. Found: C, 38.03; H, 5.48; Cl, 5.00; P, 8.73%.
Calc. for C22H39ClP2PtRu: C, 37.91; H, 5.64; Cl, 5.09;
P, 8.89%.
3.4. Preparation of trans-RcPt(PEt3)2Br (5b)
To a solution of 5a (470 mg, 0.674 mmol) in
methanol (20 ml) was added a solution of NaBr (560
mg, 5.44 mmol) in 30 ml of methanol and stirred for 3
h at r.t. After removal of the solvent in vacuo, the
residue was dissolved in 50 ml of benzene and washed
with 250 ml of water for three times. Organic layer was
dried over Na2SO4 and benzene was evaporated under
vacuum again. Recrystallization from hexane gave pale

74
T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
yellow crystals (437 mg, yield 87%). M.p. 135–136°C.
1H-NMR (CDCl3): l 4.48 (t, J=1.5 Hz, 2H, C5H4),
4.35 (s, 5H, C5H5), 4.28 (t, J=1.5 Hz, JPt–H=29.3 Hz,
2H, C5H4), 2.03–1.96 (m, 12H, CH2), 1.09 (quintet,
J=7.9 Hz, 18H, CH3). 13C-NMR (CDCl3): l 88.78 (t,
2JP–C=8.3 Hz, ipso C of C5H4), 77.92 (s, JPt–C=74.4
Hz, C5H4), 71.22 (s, C5H5), 67.72 (s, JPt–C=62.9 Hz,
C5H4), 13.14 (t, J=16.5 Hz, CH2), 8.01 (s, CH3).
5.09 (s, 2H, C5H4), 4.57 (s, 2H, C5H4), 4.52 (s, 5H,
C5H5), 1.99–1.80 (m, 12H, CH2), 1.14 (quintet, J=7.9
2
Hz, 18H, CH3). 13C-NMR (CDCl3): l 212.2 (t, JP–C
=
2
3
5.8 Hz, CO), 100.7 (t, JPt–C=261 Hz, JP–C=5.0 Hz,
ipso C of C5H4), 71.50 (s, C5H5), 71.26 (s, C5H4), 70.45
(s, C5H4), 14.72 (t, J=16.5 Hz, CH2), 7.89 (s, CH3).
31P-NMR (CDCl3): l 16.46 (s, JPt–P=3031 Hz). Anal.
1
Found: C, 36.01; H, 5.15; Br, 10.44; P, 8.05%. Calc. for
C23H39BrOP2PtRu: C, 35.90; H, 5.11; Br, 10.38; P,
8.05%.
1
31P-NMR (CDCl3): l 19.81 (s, JPt–P=2693 Hz). Anal.
Found: C, 35.84; H, 5.26; Br, 10.66; P, 8.45%. Calc. for
C22H39BrP2PtRu: C, 35.65; H, 5.30; Br, 10.78; P,
8.35%.
3.8. Reaction of trans-RcPt(PEt3)2Cl (5a) with p-tolyl
isocyanide
3.5. Preparation of trans-RcPt(PEt3)2NCS (5c)
To a 20 ml of 1,2-dichloroethane of complex 5a (152
mg, 0.218 mmol) was added p-tolyl isocyanide (31 mg,
0.26 mmol). The reaction mixture was stirred for 6 h at
reflux temperature. After removal of the solvent under
vacuum, the residue was chromatographed on alumina
using chloroform as an eluent. Yellow crystals of 9a
(111 mg, yield 63%) was obtained by recrystallization
from toluene/hexane. M.p. 182–183°C. IR (KBr):
As described in the preparation of 5b, treatment of
5a (397 mg, 0.569 mmol) with NaSCN (389 mg, 4.79
mmol) in 50 ml of acetone gave pale yellow crystals
(387 mg, yield 95%). M.p. 117–118°C. IR (KBr):
1
w(NCS) 2100 cm−1. H-NMR (CDCl3): l 4.47 (t, J=
1.2 Hz, 2H, C5H4), 4.33 (s, 5H, C5H5), 4.17 (t, J=1.2
Hz, JPt–H=25.4 Hz, 2H, C5H4), 1.91–1.84 (m, 12H,
CH2), 1.12 (quintet, J=7.9 Hz, 18H, CH3). 13C-NMR
(CDCl3): l 134.0 (s, NCS), 80.58 (s, ipso C of C5H4),
77.89 (s, JPt–C=64.5 Hz, C5H4), 71.03 (s, C5H5), 68.17
w(CꢀN) 1550 cm−1 1H-NMR (CDCl3): l 7.60 (d,
.
J=8.3 Hz, 2H, Ar), 7.06 (d, J=8.3 Hz, 2H, Ar), 5.19
(s, 2H, C5H4), 4.56 (s, 5H, C5H5), 4.55 (s, 2H, C5H4),
2.28 (s, 3H, ArCH3), 1.83–1.60 (m, 12H, CH2), 1.03
(quintet, J=7.8 Hz, 18H, PCH2CH3). 13C-NMR
(CDCl3): l 172.1 (t, 2JP–C=7.4 Hz, CꢀN), 151.2 (s,
2JPt–C=72.8 Hz, ipso C of Ar bound to –NꢀC), 133.1
(s, ipso C of Ar bound to CH3), 128.5 (s, Ar), 121.1 (s,
Ar), 101.6 (s, ipso C of C5H4), 73.31 (s, C5H4), 71.37 (s,
C5H5), 69.60 (s, C5H4), 20.87 (s, ArCH3), 14.93 (t,
J=16.5 Hz, CH2), 8.01 (s, PCH2CH3). 31P-NMR
(CDCl3): l 14.70 (s, 1JPt–P=2894 Hz). Anal. Found: C,
44.20; H, 5.72; N, 1.71; Cl, 4.22; P, 7.57%. Calc. for
C30H46NClP2PtRu: C, 44.25; H, 5.69; N, 1.72; Cl, 4.35;
P, 7.61%.
(s, JPt–C=54.6 Hz, C5H4), 13.02 (t, J=16.5 Hz, CH2),
7.88 (s, CH3). 31P-NMR (CDCl3): l 23.88 (s, JPt–P
=
1
2654 Hz). Anal. Found: C, 38.24; H, 5.46; N, 1.94; P,
8.67%. Calc. for C23H39NP2PtRuS: C, 38.36; H, 5.46;
N, 1.95; P, 8.61%.
3.6. Reaction of trans-RcPt(PEt3)2Cl (5a) with CO
A dichloromethane solution of 5a (50 mg, 0.072
mmol) was placed in 100 ml of autoclave and charged
with CO (30 kg cm−2). After standing for 24 h at r.t.,
the solvent was removed under vacuum. Pale yellow
crystals of 7a (46 mg, yield 88%) were obtained by
recrystallization of toluene/hexane. M.p. 153–154°C.
3.9. Reaction of trans-RcPt(PEt3)2Cl (5a) with
2,6-xylyl or p-nitrophenyl isocyanide
IR (KBr): w(CꢀO) 1610 cm−1 1H-NMR (CDCl3): l
.
5.09 (s, 2H, C5H4), 4.58 (s, 2H, C5H4), 4.52 (s, 5H,
C5H5), 1.93–1.75 (m, 12H, CH2), 1.15 (quintet, J=7.9
Hz, 18H, CH3). 13C-NMR (CDCl3): l 211.6 (s, CO),
101.1 (t, 3JP–C=4.1 Hz, ipso C of C5H4), 71.45 (s,
C5H5), 71.16 (s, C5H4), 70.42 (s, C5H4), 14.18 (t, J=
16.5 Hz, CH2), 7.81 (s, CH3). 31P-NMR (CDCl3): l
16.61 (s, JPt–P=3044 Hz). Anal. Found: C, 38.01; H,
5.34; Cl, 4.74; P, 8.32%. Calc. for C23H39ClOP2PtRu: C,
38.10; H, 5.42; Cl, 4.89; P, 8.54%.
These reactions were performed by a procedure simi-
lar to that with p-tolyl isocyanide.
9b: Yellow crystals, yield 36%, m.p. 198–199°C. IR
1
(KBr): w(CꢀN) 1555 cm−1. H-NMR (CDCl3): l 6.94
(d, J=7.3 Hz, 2H, Ar), 6.82 (t, J=7.3 Hz, 1H, Ar),
5.29 (s, 2H, C5H4), 4.55 (s, 2H, C5H4), 4.54 (s, 5H,
C5H5), 2.49 (s, 6H, ArCH3), 1.75–1.63 (m, 12H, CH2),
1.03 (quintet, J=7.8 Hz, 18H, PCH2CH3). 13C-NMR
(CDCl3): l 168.0 (s, CꢀN), 149.7 (s, ipso C of Ar bound
to –NꢀC), 128.5 (s, Ar), 128.3 (s, ipso C of Ar bound
to CH3), 122.4 (s, Ar), 104.5 (s, ipso C of C5H4), 73.25
(s, C5H4), 71.12 (s, C5H5), 69.01 (s, C5H4), 21.49 (s,
1
3.7. Reaction of trans-RcPt(PEt3)2Br (5b) with CO
This reaction was carried out by a procedure similar
to that of 5a.
ArCH3), 15.40 (t, J=16.5 Hz, CH2), 8.36 (s,
1
7b: Pale yellow crystals, yield 88%, m.p. 160–161°C.
PCH2CH3). 31P-NMR (CDCl3): l 13.92 (s, JPt–P
=
IR (KBr): w(CꢀO) 1590 cm−1
.
1H-NMR (CDCl3): l
2992 Hz). Anal. Found: C, 45.00; H, 5.58; N, 1.76; Cl,

T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
75
4.56; P, 7.30%. Calc. for C31H48NClP2PtRu: C, 44.95;
H, 5.84; N, 1.69; Cl, 4.28; P, 7.48%.
11b: Yellow crystals, yield 40%, m.p. 154–155°C. IR
(KBr): w(CꢀO) 1730, 1705, w (CꢀC) 1610 cm−1 1H-
.
9c: Yellow orange crystals, yield 50%, m.p. 196–
NMR (CDCl3): l 7.88 (s, 1H, ꢀCH), 4.69 (t, J=2.0 Hz,
1H, C5H3), 4.65 (s, 1H, C5H3), 4.52 (s, JPt–H=32.2 Hz,
1H, C5H3), 4.37 (s, 5H, C5H5), 3.88 (s, 3H, OCH3), 3.66
(s, 3H, OCH3), 2.56–1.98 (m, 6H, CH2), 1.69–1.63 (m,
6H, CH2), 1.21–1.13 (m, 9H, PCH2CH3), 1.03–0.95 (m,
9H, PCH2CH3). 13C-NMR (CDCl3): l 169.5 (s, CO),
166.5 (s, CO), 152.9 (s, ꢀC), 110.6 (s, ꢀCH), 89.96 (t,
2JP–C=8.3 Hz, ipso C of C5H3 bound to Pt), 84.16 (s,
2JPt–C=43.0 Hz, ipso C of C5H3 bound to –CꢀC),
81.22 (s, JPt–C=61.2 Hz, C5H3), 73.22 (s, C5H5), 70.98
(s, JPt–C=66.2 Hz, C5H3), 69.98 (s, JPt–C=46.3 Hz,
C5H3), 52.29 (s, OCH3), 51.42 (s, OCH3), 13.90 (dd,
.
197°C. IR (KBr): w(CꢀN) 1535 cm−1 1H-NMR
(CDCl3): l 8.16 (d, J=8.8 Hz, 2H, Ar), 7.70 (d, J=8.8
Hz, 2H, Ar), 5.21 (s, 2H, C5H4), 4.61 (s, 2H, C5H4),
4.56 (s, 5H, C5H5), 1.86–1.65 (m, 12H, CH2), 1.03
(quintet, J=7.9 Hz, 18H, CH3). 13C-NMR (CDCl3): l
2
3
181.0 (t, JP–C=6.6 Hz, CꢀN), 159.4 (s, JPt–C=71.1
Hz, ipso C of Ar bound to –NꢀC), 143.2 (s, ipso C of
Ar bound to NO2), 124.1 (s, Ar), 121.0 (s, Ar), 101.0 (s,
ipso C of C5H4), 73.44 (s, C5H4), 71.63 (s, C5H5), 70.31
(s, C5H4), 14.97 (t, J=16.5 Hz, CH2), 8.05 (s, CH3).
1
31P-NMR (CDCl3): l 15.52 (s, JPt–P=2809 Hz). Anal.
3
1
Found: C, 41.20; H, 5.18; N, 3.32; Cl, 4.19; P, 7.29%.
Calc. for C29H43N2ClO2P2PtRu: C, 41.21; H, 5.13; N,
3.31; Cl, 4.19; P, 7.33%.
1JP–C=21.5 Hz, JP–C=9.9 Hz, CH2), 12.30 (dd, JP–
3
C=24.8 Hz, JP–C=9.9 Hz, CH2), 7.88 (s, PCH2CH3).
31P-NMR (CDCl3): l 18.05 (d, JPt–P=2586 Hz, JP–
P=414 Hz), 16.82 (d, 1JPt–P=2652 Hz, 2JP–P=414
Hz). Anal. Found: C, 38.15; H, 5.14; Br, 9.01; P, 6.93%.
Calc. for C28H45BrO4P2PtRu: C, 38.06; H, 5.13; Br,
9.04; P, 7.01%.
1
2
3.10. Reaction of trans-RcPt(PEt3)2Cl (5a) with
dimethyl acetylenedicarboxylate (DMAD)
To a solution of 5a (126 mg, 0.180 mmol) in benzene
(20 ml) was added DMAD (26 mg, 0.18 mmol) and the
mixture was stirred at 80°C for 24 h. After removal of
the solvent in vacuo, the residue purified by chromatog-
raphy on alumina using CH2Cl2 as an eluent. Recrystal-
lization from toluene/hexane gave yellow crystals of 11a
(37 mg) in 25% yield. M.p. 166–167°C. IR (KBr):
3.12. Reaction of trans-RcPt(PEt3)2Cl (5a) with diethyl
acetylenedicarboxylate
This reaction was also carried out by a procedure
similar to that with DMAD.
11c: Yellow crystals, yield 30%, m.p. 127–128°C. IR
(KBr): w(CꢀO) 1730, 1705, w (CꢀC) 1610 cm−1 1H-
.
w(CꢀO) 1735, 1705, w(CꢀC) 1610 cm−1 1H-NMR
.
NMR (CDCl3): l 7.89 (s, 1H, ꢀCH), 4.66 (s, 1H, C5H3),
4.65 (s, 1H, C5H3), 4.52 (s, 1H, C5H3), 4.37 (s, 5H,
C5H5), 4.34 (quartet, J=7.1 Hz, 2H, OCH2), 4.12 (d
quartet, J=7.3, 2.0 Hz, 2H, OCH2), 2.50–1.94 (m, 6H,
PCH2), 1.59 (quartet, J=7.2 Hz, 6H, PCH2), 1.39 (t,
J=7.1 Hz, 3H, OCH2CH3), 1.21 (t, J=7.1 Hz,
OCH2CH3), 1.23–1.12 (m, 9H, PCH2CH3), 1.04–0.96
(m, 9H, PCH2CH3). 13C-NMR (CDCl3): l 169.0 (s,
CO), 165.9 (s, CO), 152.7 (s, ꢀC), 111.2 (s, ꢀCH), 86.82
(CDCl3): l 7.94 (s, 1H, ꢀCH), 4.67 (t, J=2.4 Hz, 1H,
C5H3), 4.63 (dd, J=1.0, 1.5 Hz, 1H, C5H3), 4.52 (s,
JPt–H=32.7 Hz, 1H, C5H3), 4.37 (s, 5H, C5H5), 3.88 (s,
3H, OCH3), 3.66 (s, 3H, OCH3), 2.48–1.95 (m, 6H,
CH2), 1.61–1.56 (m, 6H, CH2), 1.22–1.14 (m, 9H,
PCH2CH3), 1.04–0.96 (m, 9H, PCH2CH3). 13C-NMR
(CDCl3): l 169.5 (s, CO), 166.5 (s, CO), 153.0 (s, ꢀC),
2
110.7 (s, ꢀCH), 87.07 (t, JP–C=8.3 Hz, ipso C of C5H3
bound to Pt), 84.01 (s, 2JPt–C=41.4 Hz, ipso C of C5H3
bound to –CꢀC), 81.34 (s, JPt–C=56.2 Hz, C5H3),
73.03 (s, C5H5), 71.01 (s, JPt–C=67.8 Hz, C5H3), 69.89
(s, JPt–C=44.7 Hz, C5H3), 52.24 (s, OCH3), 51.35 (s,
OCH3), 13.31 (dd, 1JP–C=21.5 Hz, 3JP–C=11.6 Hz,
CH2), 11.38 (dd, 1JP–C=23.2 Hz, 3JP–C=9.9 Hz, CH2),
7.76 (s, PCH2CH3), 7.66 (s, PCH2CH3). 31P-NMR
2
(t, JP–C=8.3 Hz, ipso C of C5H3 bound to Pt), 84.19
2
(s, JPt–C=41.4 Hz, ipso C of C5H3 bound to –CꢀC),
81.16 (s, JPt–C=61.2 Hz, C5H3), 72.92 (s, C5H5), 70.86
(s, JPt–C=67.8 Hz, C5H3), 69.68 (s, JPt–C=44.7 Hz,
C5H3), 61.06 (s, OCH2), 59.82 (s, OCH2), 14.18 (s,
1
OCH2CH3), 14.05 (s, OCH2CH3), 13.22 (dd, JP–C
=
3
1
21.5 Hz, JP–C=9.9 Hz, PCH2), 11.31 (dd, JP–C=24.8
1
2
(CDCl3): l 18.75 (d, JPt–P=2605 Hz, JP–P=417 Hz),
17.68 (d, 1JPt–P=2686 Hz, 2JP–P=417 Hz). Anal.
Found: C, 40.22; H, 5.40; Cl, 4.50; P, 7.11%. Calc. for
C28H45ClO4P2PtRu: C, 40.07; H, 5.40; Cl, 4.22; P,
7.38%.
3
Hz, JP–C=9.9 Hz, PCH2), 7.73 (s, PCH2CH3), 7.60 (s,
1
PCH2CH3). 31P-NMR (CDCl3): l 18.34 (d, JPt–P
=
2
1
2611 Hz, JP–P=417 Hz), 16.95 (d, JPt–P=2686 Hz,
2JP–P=417 Hz). Anal. Found: C, 41.79; H, 5.72; Cl,
4.25; P, 7.00%. Calc. for C30H49ClO4P2PtRu: C, 41.55;
H, 5.69; Cl, 4.09; P, 7.14%.
3.11. Reaction of trans-RcPt(PEt3)2Br (5b) with
DMAD
3.13. X-ray crystallographic studies
This reaction was performed by a procedure similar
Single crystals of 3, 4, 5c and 9a suitable for an X-ray
to that of 5a.
diffraction analysis were obtained by cooling of

76
T. Yoshida et al. / Journal of Organometallic Chemistry 574 (1999) 66–76
References
CH2Cl2/hexane solution of 3 at −10°C, slow evapo-
ration of CH2Cl2 solution of 4 at r.t., slow evapora-
tion of hexane solution for 5c at r.t. and cooling of
toluene/hexane solution at −10°C for 9a, respec-
tively, and mounted on glass fibers with epoxy resin.
Diffraction measurements were made on a Rigaku
AFC5R diffractometer with graphite monochromated
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Acknowledgements
This work is supported by Grant-in-Aid for Scien-
tific Research from The Ministry of Education, Sci-
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.