Selective C-C bond activation of 2-aryl-1-methylenecyclopropanes promoted by Ir(I) and Rh(I) hydrido complexes. Mechanism of ring-opening isomerization of the strained molecules

Article abstract of DOI:10.1246/bcsj.78.1469

[IrH(CO)(PPh₃)₃] promotes ring opening of 2-phenyl-1-methylenecyclopropane at room temperature to produce the Ir complex with a chelating 2-phenyl-3-butenyl ligand, [Ir{η₂-CH ₂CH(Ph)CH=CH₂-κC¹

Full text of DOI:10.1246/bcsj.78.1469

Ó 2005 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 78, 1469–1480 (2005) 1469
Selective C–C Bond Activation of 2-Aryl-1-methylenecyclopropanes
Promoted by Ir(I) and Rh(I) Hydrido Complexes. Mechanism
of Ring-Opening Isomerization of the Strained Molecules
ꢀ
Yasushi Nishihara, Chikako Yoda, Masumi Itazaki, and Kohtaro Osakada
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503
Received March 7, 2005; E-mail: kosakada@res.titech.ac.jp
[IrH(CO)(PPh3)3] promotes ring opening of 2-phenyl-1-methylenecyclopropane at room temperature to produce
the Ir complex with a chelating 2-phenyl-3-butenyl ligand, [Ir{ꢀ2-CH2CH(Ph)CH=CH2-ꢁC1}(CO)(PPh3)2] (1). The re-
action of excess 2-phenyl-1-methylenecyclopropane with [IrH(CO)(PPh3)3] at 50 ꢁC yields [Ir{ꢀ2-(o-C6H4)CH(Me)CH=
CH2-ꢁC1}(CO)(PPh3)2] (2), accompanied by the formation of 1-phenyl-1,3-butadiene and 2-phenyl-1,3-butadiene. 2,2-
Diphenyl-1-methylenecyclopropane reacts with [IrH(CO)(PPh3)3] to afford [Ir{ꢀ2-CH2CPh2CH=CH2-ꢁC1}(CO)-
ꢁ
ꢁ
(PPh3)2] ꢁ(3) at 50 C and [Ir{ꢀ2-(o-C6H4)CMe(Ph)CH=CH2-ꢁC1}(CO)(PPh3)2] (4) at 100 C. Heating a solution of
3 at 100 C also forms 4 quantitatively. X-ray crystallography of 3 reveals a penta-coordinated structure around the Ir
center bonded to a chelating 2,2-diphenyl-3-butenyl ligand. The reactions of 2,2-diphenyl-1-methylenecyclopropane and
of 2,2-di(4-fluorophenyl)-1-methylenecyclopropane with [RhH(CO)(PPh3)3] at room temperature yield [Rh{ꢀ2-
CH2CAr2CH=CH2-ꢁC1}(CO)(PPh3)2] (5a: Ar ¼ Ph, 5b: Ar ¼ C6H4-F-4). The reactions at 50 C cause ring opening
ꢁ
of the substrate and orthometalation of the phenyl group to afford [Rh{ꢀ2-(o-C6H4)CMe(Ph)CH=CH2-ꢁC1}-
(CO)(PPh3)2] (6a) and [Rh{ꢀ2-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-ꢁC1}(CO)(PPh3)2] (6b), respectively. Formation
of 1,1-diaryl-1,3-butadiene is observed during the reaction. Heating a solution of 5a at 50 ꢁC produces 1,1-diphenyl-1,3-
butadiene and an allylrhodium complex, 8, rather than 6a, although the reaction of excess 2,2-diphenyl-1-methylene-
cyclopropane with 5a at 50 ꢁC affords 6a in 60%. The mechanisms of the above reactions are discussed based on
the products and reaction rates. Coordination of P(OMe)3 to the Rh center of 5a causes insertion of the CO ligand into
the Rh–C bond to afford [Rh{ꢀ2-CO-CH2CPh2CH=CH2-ꢁC1}(P(OMe)3)3] (7).
Methylenecyclopropanes, which have high strain energy
(ꢀHf larger than that of cyclopropane by approximately 35
kcal molꢂ1),1,2 have been utilized as the substrates of synthetic
organic reactions3–23 and polymer synthesis24–32 catalyzed by
transition metal complexes. Reactions of methylenecyclopro-
panes with transition metal complexes lead to the formation
of unique products such as 1,3-dienes via ring-opening isomer-
ization (Ni and Sc),33,34 cyclopropylmethyl complexes via
insertion of C=C bond into hydride–metal bond (Pd),35,36
and metallacycle via co-dimerization with olefin (Ti).37,38
Previously we reported that 2-aryl-1-methylenecyclopropane
reacted with [RhCl(PPh3)3] to produce the Rh complexes with
ꢂ-coordinated methylenecyclopropanes, [RhCl(ꢀ2-CH2=
CCH(Ar)CH2)(PPh3)2], and that the complexes having a 1,3-
diene ligand, [RhCl(ꢀ2,ꢀ2-CH2=C(Ar)CH=CH2)(PPh3)2],
are formed via isomerization of the ꢂ-coordinated methylene-
cyclopropanes.39,40 In this paper, we report the reactions of sub-
stituted 1-methylenecyclopropanes with hydride complexes of
Rh and Ir, in which stepwise ring-opening isomerization takes
place via selective C–C bond cleavage of the cyclopropane
ring and the subsequent C–H bond activation of the ligand.
A part of this work was reported in a preliminary form.41
3-butenyliridium(I) complex, [Ir{ꢀ2-CH2CH(Ph)CH=CH2-
ꢁC1}(CO)(PPh3)2] (1, 88%) at room temperature (Eq. 1).
O
C
Ph3P
IrH(CO)(PPh )
+
Ir
3 3
H
H
ð1Þ
Ph3P
rt, 24 h
Ph
Ph
1
:
2.4
1
88%
The reaction of excess 2-phenyl-1-methylenecyclopropane
at 50 ꢁC gives a mixture of [Ir{ꢀ2-(o-C6H4)CH(Me)CH=
CH2-ꢁC1}(CO)(PPh3)2] (2, 82%), 2-phenyl-1,3-butadiene
(470%/Ir), and 1-phenyl-1,3-butadiene (177%/Ir) (Eq. 2).
IrH(CO)(PPh3)3
1
+
H
Ph
:
10
Ph
O
C
ð2Þ
Ph3P
Ph3P
470% / Ir
Ir
+
Me
50 °C, 40 h
Ph
177% / Ir
2
82%
Results and Discussion
Reaction of 2-Phenyl-1-methylenecyclopropane with
[IrH(CO)(PPh3)3]. The reaction of 2-phenyl-1-methylene-
cyclopropane with [IrH(CO)(PPh3)3] produces the 2-phenyl-
Once isolated, 1 is stable in the solid state and in a solution
containing 2-phenyl-1-methylenecyclopropane, but dissolution
of it in benzene-d6 results in partial isomerization into 2 even
Published on the web August 4, 2005; DOI 10.1246/bcsj.78.1469

1470 Bull. Chem. Soc. Jpn., 78, No. 8 (2005)
C–C Bond Activation by Rh and Ir
at room temperature.
H
OC
Ir
H
CO
Crystallographic structures of 1 and 2 were reported in the
preceding communication.41 Both complexes have distorted
trigonal bipyramidal coordination around the Ir center. A
chelating coordination of the 2-phenyl-3-butenyl ligand of 1
resembles that of the 2,2-di(phenylethyl)-3-butenyl ligand
of [Rh{ꢀ2-CH2C(CH2CH2Ph)2CH=CH2-ꢁC1}(CO)(PPh3)2].42
The Ir–C bond distances of the vinylic group of the 2-phenyl-
H
H
PPh3
Ph3P
Ph3P
PPh3
Ir
H
H
Me
H
H
Me
2
2'
ꢁ
3-butenyl ligand are 2.14(1) A and 2.12(2) A. The C=C bond
ꢁ
distance (1.33(2) A) is close to the length of the corresponding
ꢁ
Scheme 1.
bonds of the complexes with a tethered C=C functionality,
43,44
ꢁ
(1.34–1.40 A).
ꢁ
The C=C bond (1.439(9) A) of 2 is elon-
gated more significantly by the coordination, this is ascribed
to the absence of a ligand at the coordination site trans to
the vinyl ligand.
1
The H NMR spectrum of 1 exhibits the Ir–CH2 hydrogen
signals at ꢃ 0.11 and 1.70, the latter of which is overlapped
with the signal of an olefinic hydrogen. The signals at ꢃ
1.70, 1.81, and 2.96 are assigned to the hydrogens of the
CH=CH2 group based on the 1H–1H COSY spectrum. The vi-
nyl hydrogen signals appear at higher magnetic field than those
of CH=CH2 group of organic molecules (ꢃ 4.5–7.0), similarly
to the olefin complexes of transition metals.45 The CH hydro-
gen signal at ꢃ 4.48 shows coupling with the two CH2 hydro-
gens. The 13C{1H} NMR spectrum of 1 contains the signals at
ꢃ ꢂ12:4 and 28.2 due to the carbons of the Ir–CH2–CH group.
The resonances of the =CH2 and CH= carbons at ꢃ 31.2 and
28.2 are close to the positions expected for the carbons of a co-
ordinated olefin (ꢃ 40–85).46 The presence of a carbonyl ligand
is evidenced by the 13C{1H} NMR signal at low field position
(ꢃ 185.8) and by the IR band at a characteristic position (1939
cmꢂ1).
The 1H NMR spectrum of 2 displays a doublet of the methyl
hydrogens at ꢃ 1.53 and the signals due to four hydrogens of
the 1-methylallyl group at ꢃ 1.79, 2.85, and 3.48. Small signals
are observed at ꢃ 2.97 and 3.69, which can be assigned to a mi-
nor isomer of 2 (vide infra). The 13C{1H} NMR signals of the
coordinated vinyl group at ꢃ 28.1 and 55.3 are split due to cou-
pling with two phosphorus nuclei. The phenyl carbon signals
of the 2-(1-methylallyl)phenyl ligand at ꢃ 122.5, 124.5,
124.7, 141.2, 150.1, and 154.2 show small 31P–13C coupling
constants (2–12 Hz). The 31P{1H} NMR spectrum of 2 exhibits
two doublets at ꢃ 0.36 and 3.31 (JðP{PÞ ¼ 43:4 Hz) and anoth-
er pair of doublets at ꢃ 1.66 and 4.28 (JðP{PÞ ¼ 40:1 Hz) in
much smaller intensities, indicating the presence of a minor
isomer in solution. Positions of the 13C{1H} NMR signals
and of a part of the 1H NMR signals are not determined unam-
biguously due to the low peak intensity and/or overlapping
with other signals. The NMR spectra of the solution of 2,
which can be isolated as single crystals show the presence of
the two isomers, which indicates isomerization of 2 in the so-
lution. Scheme 1 depicts the structure of 2 determined by X-
ray crystallography and that of its possible diastereomer 20.
The two species observed in the solution may be attributed
to these isomers.
Fig. 1. Structure of complex 3 determined by X-ray crystal-
lography with 50% thermal ellipsoidal plotting. Hydrogen
atoms at the aromatic rings were omitted for simplicity.
cies, but this could not be interpreted by simple interconver-
sion of the two species.
Reaction of 2,2-Diphenyl-1-methylenecyclopropane with
[IrH(CO)(PPh3)3]. Although the reaction of 2,2-diphenyl-1-
methylenecyclopropane with [IrH(CO)(PPh3)3] does not occur
at room temperature, heating the mixture to 50 ꢁC forms
[Ir{ꢀ2-CH2CPh2CH=CH2-ꢁC1}(CO)(PPh3)2] (3) in 78%
yield after 15 h (Eq. 3). The reaction of 2,2-diphenyl-1-meth-
ylenecyclopropane with [IrH(CO)(PPh3)3] at 100 ꢁC affords
[Ir{ꢀ2-(o-C6H4)CMe(Ph)CH=CH2-ꢁC1}(CO)(PPh3)2] (4) in
80% yield (Eq. 4).
O
C
Ph3P
IrH(CO)(PPh3)3
1
+
Ph
Ph
Ir
Ph
Ph
ð3Þ
50 °C, 15 h
Ph3P
:
2.5
3
78%
O
C
Ph
Me
Ph3P
Ph3P
IrH(CO)(PPh3)3
1
+
Ir
Ph
Ph
100 °C, 48 h
ð4Þ
:
2.5
4
80%
Complex 3 was characterized by X-ray crystallography and
NMR spectroscopy. The molecular structure of 3 in Fig. 1
indicates a distorted trigonal bipyramidal coordination with
PPh3 and CH2 groups at the apical sites.
ꢁ
The C=C double bond (C4{C5 ¼ 1:434ð9Þ A) is elongated
Isomerization between 2 and 20 should occur via decoordi-
nation of the vinyl group, rotation of the C–C bond of the li-
gand, and re-coordination of the vinyl group. Temperature de-
pendent NMR spectra suggest fluxional behavior of the spe-
from uncoordinated C=C double bond. The H NMR signals
of 3 at ꢃ 1.63, 1.75, and 3.00 are assigned to the olefinic hydro-
1
1
gens based on the H–1H COSY spectrum. The diastereotopic
methylene protons of the CH2 group bonded to iridium appear

Y. Nishihara et al.
Bull. Chem. Soc. Jpn., 78, No. 8 (2005) 1471
at ꢃ ꢂ0:70 and 1.93. The 13C{1H} NMR spectrum shows a sig-
nal of the CH2 carbon at ꢃ ꢂ7:0 with a large coupling constant
(JðC{PÞ ¼ 62:0 Hz). A carbonyl carbon signal at ꢃ 184.9 cou-
ples with two phosphorus nuclei with coupling constants of
14.4 and 7.5 Hz.
Complex 4 shows the 1H NMR signals for three olefinic
1
protons at ꢃ 0.72, 1.43, and 2.73. The H NMR (ꢃ 1.94) and
13C{1H} NMR (ꢃ 29.5) signals of the methyl group are ob-
served at reasonable positions. The 13C{1H} NMR spectrum
shows the signal of carbonyl carbon at ꢃ 185.4 with JðC{PÞ ¼
12:2, 10.5 Hz. Heating a toluene solution of 3 at 100 ꢁC leads
to its clean conversion into 4 (Eq. 5).
O
C
O
C
Ph
Me
Ph3P
Ph3P
Ph3P
Ph3P
Fig. 2. Arrhenius plot of the first-order rates constant for
thermal isomerization of 3 into 4.
Ir
Ir
Ph
Ph
ð5Þ
100 °C, 48 h
3
4
quant.
Such a process indicates that formation of 4 in reaction (4)
involves initial formation of 3 and its thermally induced C–H
bond activation. The reaction is followed by a change of the
1H NMR signal intensity, which indicates first-order kinetics
with kobs (sꢂ1) ¼ 3:19 ꢃ 10ꢂ4 (358 K), 5:97 ꢃ 10ꢂ4 (363 K),
8:22 ꢃ 10ꢂ4 (368 K), and 1:52 ꢃ 10ꢂ3 (373 K). Figure 2
shows Arrhenius plots of the reaction, giving the activation
energy of Ea ¼ 111:2 kJ molꢂ1
.
Reactions of 2,2-Diaryl-1-methylenecyclopropanes with
[RhH(CO)(PPh3)3]. The reactions of 2,2-diphenyl-1-methyl-
enecyclopropane and of 2,2-di(4-fluorophenyl)-1-methylene-
cyclopropane with [RhH(CO)(PPh3)3] at room temperature
give Rh(I) complexes with 2,2-diaryl-3-butenyl ligands,
[Rh{ꢀ2-CH2CPh2CH=CH2-ꢁC1}(CO)(PPh3)2] (5a), and
[Rh{ꢀ2-CH2C(C6H4-F-4)2CH=CH2-ꢁC1}(CO)(PPh3)2] (5b),
respectively (Eq. 6).
Fig. 3. 1H NMR spectra of the reaction of 2,2-diphenyl-1-
methylenecyclopropane with [RhD(CO)(PPh3)3] in ben-
zene-d6 after 1 h. Signals with an asterisk are assignable
to 2,2-diphenyl-1-methylenecyclopropane. H NMR spec-
tra (in benzene) of the same sample (upper right).
2
ligand to the trigonal bipyramidal Rh center is similar to the
structures of 1 and 3. Table 1 compares the bond parameters
of these complexes and of [Rh{ꢀ2-CH2C(CH2CH2Ph)2-
+
RhH(CO)(PPh3)3
1
Ar
Ar
1
CH=CH2-ꢁC1}(CO)(PPh3)2].42 The H NMR spectrum of 5a
:
1.1
O
C
exhibits resonances of the olefinic protons at ꢃ 2.20, 2.36,
and 3.43, which are at slightly lower magnetic field positions
than the corresponding signals of 1 (ꢃ 1.70, 1.81, and 2.96).
The signals due to Rh–CH2 hydrogens are observed at ꢃ
0.52 and 1.87. The 13C{1H} NMR spectrum of 5a shows the
signal of the Rh–CH2 carbon at ꢃ 6.1. The signals of the ole-
finic carbons (ꢃ 51.0 and 59.0) are shifted to lower field posi-
tions compared with 1 (ꢃ 28.2 and 31.2). The IR spectrum
demonstrates terminal carbonyl stretching (ꢅðCOÞ ¼ 1952
cmꢂ1), which is consistent with the 13C{1H} NMR spectrum,
showing a carbonyl carbon signal at ꢃ 201.2 (JðRh{CÞ ¼ 71
Hz, JðC{PÞ ¼ 16 and 12 Hz). Accordingly, 2,2-di(4-fluoro-
phenyl)-1-methylenecyclopropane reacts with [RhH(CO)-
(PPh3)3] to yield [Rh{ꢀ2-CH2C(C6H4-F-4)2CH=CH2-ꢁC1}-
(CO)(PPh3)2] (5b) in 93% yield. The 1H spectrum of 5b at
room temperature is very similar to that of 5a, although facile
isomerization of 5b into the isomer with 2-allylphenyl ligand
(vide infra) prevents measurement of its 13C{1H} NMR spec-
trum.
Ph3P
Ph3P
ð6Þ
Rh
Ar
rt , 1 h
Ar
5a: Ar = Ph
75%
5b: Ar = C6H4F-4 93%
The reaction of 2,2-diphenyl-1-methylenecyclopropane
with [RhD(CO)(PPh3-d15)3] gives complex 5a containing
deuterium at ꢄ-position of the 2,2-diphenyl-3-butenyl ligand.
Figure 3 shows the H and H NMR spectra of the product.
The 1H NMR signal at ꢃ 3.43 due to a vinyl hydrogen
(=CH–) is much lower than the signals of other vinyl hydro-
gens (=CH2). The H NMR spectrum exhibits a broad signal
at the same position owing to selective deuteration at the posi-
tion. The content of the introduced deuterium is calculated as
1
2
2
1
87% from the H NMR peak area ratio.
The molecular structure of 5a was determined by X-ray
crystallography.41 Coordination of the chelating 3-butenyl

1472 Bull. Chem. Soc. Jpn., 78, No. 8 (2005)
C–C Bond Activation by Rh and Ir
ꢁ
Table 1. Selected Bond Distances (A) and Angles (deg) for 2,2-Diaryl-3-butenyl Complexes
5a (M ¼ Rh) [Rh(ꢀ2-CH2CR2CH=CH2)-
1 (M ¼ Ir)
3 (M ¼ Ir)
(CO)(PPh3)2] (R: CH2CH2Ph)
M–P1
M–P2
M–C1
M–C2
M–C4
M–C5
C2–C3
C3–C4
C4–C5
C1–O1
2.385(4)
2.341(1)
1.65(3)
2.11(1)
2.14(1)
2.12(5)
1.54(2)
1.48(2)
1.33(2)
1.31(3)
2.377(2)
2.361(2)
1.860(7)
2.155(6)
2.150(5)
2.162(6)
1.565(8)
1.592(9)
1.434(9)
1.148(7)
2.408(4)
2.375(2)
2.353(2)
1.881(7)
2.162(6)
2.132(6)
2.157(6)
1.534(8)
1.520(8)
1.441(9)
1.146(7)
2.376(4)
1.89(1)
2.13(1)
2.12(1)
2.16(1)
1.52(2)
1.54(2)
1.36(2)
1.13(1)
P1–M–P2
M–C1–O1
M–C2–C3
M–C4–C3
M–C4–C5
M–C5–C4
C2–C3–C4
C3–C4–C5
106.6(1)
167(2)
94.7(8)
95(1)
71(1)
72(1)
101.04(6)
178.4(6)
95.8(4)
95.2(4)
71.0(4)
70.1(3)
96.6(5)
117.1(6)
100.6(1)
179(1)
96.0(8)
95.8(8)
72.9(8)
70.0(8)
97(1)
102.49(6)
178.2(6)
96.6(4)
98.2(4)
71.3(4)
98.2(4)
97.5(5)
117.0(6)
98(1)
120(2)
116(1)
Ref.
41
this work
41
42
The reaction of 2,2-diphenyl-1-methylenecyclopropane
and [RhH(CO)(PPh3)3] in a 5:1 molar ratio in toluene at 50
ꢁC gives [Rh{
(6a) (Eq. 7).
ꢀ
2-(o-C6H4)CMe(Ph)CH=CH2-
ꢁ
C1}(CO)(PPh3)2]
+
RhH(CO)(PPh3)3
Ar
Ar
1
1
:
:
5
3
O
C
ð7Þ
Ph3P
Ph3P
Ar
Me
Ar
Rh
+
Ar
50 °C
Fig. 4. Structure of 6b determined by X-ray crystallogra-
phy with 50% thermal ellipsoidal plotting. One of the
two crystallographically independent molecules is shown.
Hydrogen atoms at the aromatic rings and solvents were
omitted for simplicity.
X
(36 h)
(24 h)
6a: Ar = Ph, X = H
85%
395% / Rh
80% / Rh
6b: Ar = C6H4F-4, X = F 95%
NMR experiments in benzene-d6 indicated that the resulting
reaction mixture contained 6a in 85% and 1,1-diphenyl-1,3-
butadiene in 395%/Rh, respectively. The analogous complex
with fluorophenyl groups, [Rh{ꢀ2-(o-C6H3-F-4)CMe(C6H4-
F-4)CH=CH2-ꢁC1}(CO)(PPh3)2] (6b), is formed similarly.
Figure 4 shows ORTEP diagram of 6b which has a distorted
trigonal bipyramidal structure, having a phosphorus atom
(P1) and an ortho carbon of the phenyl ring at the apical posi-
tions and the other phosphorus atom (P2), a carbonyl group,
and the vinyl group at the equatorial positions.
6a shows the hydrogens of the CH=CH2 moiety at ꢃ 1.87,
2.67, and 4.13 in 1:1:1 peak area ratio. The resonance at ꢃ
2.07 is assigned to the methyl group hydrogens. A minor signal
due to the methyl hydrogens is observed at ꢃ 2.40. Since the
peak area ratio between the two peaks due to methyl hydro-
gens varies reversibly with temperature, the two isomers are
equilibrated in the solution. In the 13C{1H} NMR spectrum,
the resonance for the carbonyl carbon appears at ꢃ 200.5.
The 31P{1H} NMR spectrum of 6a shows two sets of doublets
of doublets at ꢃ 28.9 and 31.6 arising from two inequiva-
lent phosphorus atoms coupling to the rhodium center
(JðRh{PÞ ¼ 113:5 and 78.3 Hz, respectively) and to each other
(JðP{PÞ ¼ 15:7 Hz). Another pair of doublets of doublets
assigned to the minor isomer was observed at ꢃ 28.4
The coordination of 6b is in sharp contrast with 2 that has a
CO and the ortho phenyl carbon at the apical positions of the
trigonal bipyramidal coordination (Table 2).
NMR spectra of 6a indicate the presence of two isomers in
1
solution, similarly to 2 (Scheme 1). The H NMR spectrum of

Y. Nishihara et al.
Bull. Chem. Soc. Jpn., 78, No. 8 (2005) 1473
ꢁ
Table 2. Selected Bond Distances (A) and Angles (deg) for
2-Allylphenyl Complexes
2 (M ¼ Ir)
6b (M ¼ Rh)
M–P1
M–P2
M–C1
M–C2
M–C5
M–C6
C2–C3
C3–C4
C4–C5
C5–C6
C1–O1
2.377(2)
2.358(2)
1.869(6)
2.126(6)
2.161(7)
2.144(7)
1.408(8)
1.505(9)
1.509(9)
1.439(9)
1.163(7)
2.386(3)
2.424(3)
1.85(1)
2.083(9)
2.158(9)
2.16(1)
1.38(1)
1.52(1)
1.52(1)
1.39(1)
1.15(1)
Fig. 5. Structure of 7 determined by X-ray crystallography
with 50% thermal ellipsoidal plotting. Hydrogen atoms at
the aromatic rings were omittedꢁfor simplicity. Selected
ꢁ
bond distances (A) and angles ( ): Rh(1)–P(1) 2.347(2),
Rh(1)–P(2) 2.291(2), Rh(1)–P(3) 2.286(2), Rh(1)–C(1)
2.066(6), Rh(1)–C(4) 2.169(5), Rh(1)–C(5) 2.152(6),
O(1)–C(1) 1.206(6), C(1)–C(2) 1.532(8), C(2)–C(3)
1.535(8), C(3)–C(4) 1.521(7), and C(4)–C(5) 1.426(7);
P(1)–Rh(1)–P(2) 93.18(7), P(2)–Rh(1)–P(4) 93.95(6),
P(1)–Rh(1)–P(3) 102.92(6), Rh(1)–C(1)–O(1) 128.4(5),
Rh(1)–C(1)–C(2) 114.6(4), O(1)–C(1)–C(2) 117.0(5),
C(1)–C(2)–C(3) 113.8(5), C(2)–C(3)–C(4) 106.2(5),
Rh(1)–C(4)–C(3) 114.0(4), Rh(1)–C(4)–C(5) 70.1(3),
C(3)–C(4)–C(5) 119.1(5), and Rh(1)–C(5)–C(4) 71.4(3).
P1–M–P2
M–C1–O1
M–C2–C3
M–C5–C4
M–C5–C6
M–C6–C5
C2–C3–C4
C3–C4–C5
C4–C5–C6
113.10(6)
172.9(7)
115.4(5)
111.4(5)
69.8(4)
101.08(9)
177(1)
116.1(7)
113.2(6)
71.1(6)
71.1(4)
71.3(6)
116.8(6)
104.5(6)
121.6(6)
119.3(8)
106.7(7)
121.4(9)
Ref.
41
this work
Thermally Induced Isomerization of 5a. As mentioned
above, the isolated 2,2-diphenyl-3-butenyl Ir complex 3 under-
goes clean thermal isomerization into 4. The reaction of 2,2-di-
phenyl-1-methylenecyclopropane with [RhH(CO)(PPh3)3] at
(JðRh{PÞ ¼ 116:5 and JðP{PÞ ¼ 15:7 Hz) and 29.7 (JðRh{
PÞ ¼ 78:3 and JðP{PÞ ¼ 15:7 Hz).
Complex 5a reacts with P(OMe)3 to produce [Rh{ꢀ2-CO-
CH2CPh2CH=CH2-ꢁC1}(P(OMe)3)3] (7, 88%) (Eq. 8).
ꢁ
50 C produces 5a, having a similar structure to 3, accompa-
nied by generation of 1,3-dienes. Heating the isolated 3-buten-
O
C
ꢁ
ylrhodium complex 5a at 50 C does not produce the corre-
Ph3P
sponding 2-allylphenylrhodium complex 6a at all, as shown
in Eq. 9, although the reaction of excess 2,2-diphenyl-1-meth-
ylenecyclopropane with [RhH(CO)(PPh3)3] affords 6a in high
yield (Eq. 7). The Rh-containing product of thermal reaction of
5a is not isolated from the reaction mixture, and this is as-
signed tentatively to allylic rhodium complex 8 based on the
1H NMR spectrum of the solution (vide infra). Formation of
1,1-diphenyl-1,3-butadiene in 44% yield is also noted.
+
P(OMe)3
Rh
Ph
Ph
Ph3P
5a
(MeO)3P
(MeO)3P
ð8Þ
Ph
Ph
Rh
(MeO)3P
rt, 22 h
O
7
88%
O
C
Migratory insertion of CO ligand into the Rh–C bond of 5a
ocurrs during the reaction. Figure 5 depicts the molecular
structure of 7 determined by X-ray crystallography.
Ph3P
Ph3P
additive
C6D6
50 °C, 24 h
Rh
Ph
Ph
5a
The complex has a distorted trigonal bipyramidal around the
Rh center with a P(OMe)3 ligand and the CO ligand at the ap-
Me
O
O
ꢁ
ical positions. The C=C bond (1.426(7) A) is comparable to 2
C
C
Ph3P
Ph3P
Ph
+
Ph
1
Ph
+
ꢁ
ꢁ
(1.439(9) A) and 3 (1.434(9) A). The H NMR spectrum of 7
shows three hydrogen signals assigned to the CH=CH2 group
at ꢃ 2.39, 2.67, and 4.56; these are shifted to downfield com-
pared to those of the parent 5a (ꢃ 0.52, 1.87, and 3.43, respec-
tively). The appearance of three sets of doublet of doublets of
doublets in the 31P{1H} NMR spectrum of 7 indicates that the
three P(OMe)3 are magnetically inequivalent and do not un-
dergo mutual exchange in solution. Jun demonstrated that
the P(OMe)3 promoted skeletal rearrangement of the 4-penten-
ylrhodium complex into cyclobutylmethyl complexes via a
four-membered-ring recyclization.47–50
Rh
Ph3P
Me
Rh
Ph
Ph
Ph3P
ð9Þ
6a
8
NMR Yield (%)
additive
none
6a
8
butadiene
44
0
60
24
53
0
5
439
59
Ph
Ph
PPh3
0

1474 Bull. Chem. Soc. Jpn., 78, No. 8 (2005)
C–C Bond Activation by Rh and Ir
H(D)
C4
LnM
C1 C2
H
H
+
LnM H(D)
H
H
Ph
C3
M = Rh, Ir
L = PPh3, CO
Ph
Ph
Ph
A
H
C1
H
H
LnM
C2
H
H
C1
H
H
C2
C1 C2
H
H
C4
H
C4
H
H
LnM
3 Ph
Ph
C3
H
Ph Ph
+
C3
LnM
C
C4
Ph
Ph
H
H
A
B1
B2
H
H
C1
C1
C4
H
H
H
C2
H
C2
C3
H
Ph
∆
C3
C4
Ph
Ph
LnM
LnM
H
H
H
H
B1
C
H
C1
H
Ph
C3
C2
C4
H
H
H
C2
H
+
C1
H
C4
H
Ph
LnM H
LnM
C3
Ph Ph
H
B2
Scheme 2.
Addition of 5 equiv of 2,2-diphenyl-1-methylenecyclopropane
before heating the solution of 5a produces 6a in 60% yield,
along with 1,1-diphenyl-1,3-butadiene in 439% yield based
on Rh. Thermal reaction of 5a in the presence of PPh3 also
yields 6a (24%) and 1,1-diphenyl-1,3-butadiene (59%).
The Rh complex obtained from the thermal reaction of 5a
without the additives is not isolated from the reaction mixture.
The reaction of 1,1-diphenyl-1,3-butadiene with [RhH(CO)-
(PPh3)3] affords the same complex 8 (Eq. 10)
in Scheme 2. Insertion of the C=C double bond of 2,2-diaryl-
1-methylenecyclopropane into a M–H bond forms the inter-
mediate complex A having a cyclopropylmethyl ligand.35,36
Cleavage of the C–C bond of the three-membered ring via
ꢇ-alkyl elimination leads to the intermediate B1 having a
2,2-diphenyl-3-butenyl ligand and B2 having a 1,1-diphenyl-
3-butenyl ligand. ꢇ-Alkyl elimination of alkyl transition metal
complexes58 has become common in the reactions of late tran-
sition metal complexes.59–67 Cycloalkylmethyl complexes of
transition metals undergo ring opening accompanied by C–C
bond clevage, which is mentioned below. Isomerization be-
tween the Co complexes with 1-methyl-3-butenyl ligand and
with 2-methyl-3-butenyl ligand involves an intermediate
cyclopropylmethyl complex which undergoes cleavage of the
C–C bond of the three-membered ring.68,69 Casey reported
the reaction of methylenecyclobutane with a yttrium hydrido
complex to give a 4-pentenylyttrium complex via cyclobutyl-
methylyttrium intermediate.70 Flood studied the reaction of
4-pentenylplatinum complexes in detail and proposed revers-
ible formation of cyclobutylplatinum complex and its ring
opening to account for the scrambling of labeled deuteri-
um.44,71,72 Similar reactions were proposed in the cyclization
and ring opening of organic ligands catalyzed by Th and Pd
complexes.73,74
Ph
+
RhH(CO)(PPh3)3
Ph
50 °C
Me
ð10Þ
Me
O
C
Ph
Ph
Ph3P
OC
Ph
or
Ph3P
Rh
Rh
Ph
PPh3
Ph3P
8
1
which is characterized in situ by the H NMR spectroscopy.
Heating a mixture of 1,1-diphenyl-1,3-butadiene and [RhH-
(CO)(PPh3)3] in toluene-d8 leads to generation of new signals
at ꢃ 1.14 (dd, J ¼ 3:9, 6.3 Hz), 2.93 (m), and 5.61 (dd, J ¼ 2:0,
12.7 Hz) in a 3:1:1 ratio, suggesting the formation of an allylic
complex, although the present data are not sufficient to choose
the coordination mode between ꢂ-allylic and ꢆ-allylic51,52
bond. Although we could not exclude the ꢆ-allylrhodium
structure for the complex, similar Rh and Ir complexes with
ꢂ-allylic ligands were isolated and well characterized.53–56
Interconversion between the ꢆ-allyl and ꢂ-allyl Rh complex
was discussed based on the results of copolymerization of sub-
stituted allenes with CO catalyzed by Rh complexes.57
Selectivity of the reactions in Scheme 3 is explained as fol-
lows. Cleavage of less sterically demanding C–C bond occurs
easily to produce B1, while the sterically hindered C–C bond
cleavage leads to the formation of B2. The complexes 3
(M ¼ Ir) and 5a (M ¼ Rh), which correspond to B1 in Scheme
3, are isolated from the reaction mixtures. The 1,1-diphenyl-
3-butenyl complexes, having the structure of B2, were not
obtained in the reactions in Eqs. 3, 4, 6, and 7. The reaction
of 2,2-diphenyl-1-methylenecyclopropane with [RhH(CO)-
Reaction Mechanism. A plausible reaction mechanism for
the reaction of 2,2-diaryl-1-methylenecyclopropanes is shown

Y. Nishihara et al.
Bull. Chem. Soc. Jpn., 78, No. 8 (2005) 1475
(PPh3)3] (Eq. 6) accompanies formation of 1,1-diphenyl-1,3-
butadiene, which is the product of ꢇ-hydrogen elimination of
the complex B2 (M ¼ Rh). The complex B2 that formed in
the reaction with [RhH(CO)(PPh3)3] is probably turned into
[RhH(CO)(PPh3)3] by ꢇ-hydrogen elimination of the 3-
butenyl ligand to release 1,3-butadiene. The reaction with
[IrH(CO)(PPh3)3] (Eq. 4) does not form 1,3-diene nor the com-
plex having the structure with a 1,1-diphenyl-3-butenyl ligand
even at elevated temperature.
Several other rearrangements of cycloalkylmethyl-metal com-
plexes, via concerted mechanisms have been reported.
The mechanism for the C–C bond activation of 2-phenyl-1-
methylenecyclopropane is summarized in Scheme 4. C–C bond
cleavage of the cyclopropylmethyl complexes of Ir, D1 and D2,
take place similarly to the reactions of 2,2-diphenyl-1-methyl-
enecyclopropane with [IrH(CO)(PPh3)3]. D1 undergoes ther-
mally induced orthometalation of the 2-phenyl-3-butenyl
ligand to produce E or undergoes ꢇ-hydrogen elimination of
the ligand to give 2-phenyl-1,3-butadiene. The former product
E corresponds to 2 in Eq. 2. ꢇ-Hydrogen elimination of D2 re-
leases 1-phenyl-1,3-butadiene. Hydrido iridium species formed
by ꢇ-hydrogen elimination of D1 and D2 reacts further with 2-
phenyl-1-methylenecyclopropane in the reaction mixture.
Both Scheme 3 and Scheme 5 include the thermal rear-
rangement of 2-phenyl or 2,2-diphenyl-3-butenyl ligands
bonded to the metal center to 2-(1-methylallyl)phenyl ligand
via orthometalation of the phenyl group of the ligand. The
formation is considered to proceed via the pathway shown in
Scheme 5.
The absence of the intermediate B2 or its product is
explained by assuming the following equilibrium between
the intermediates B1 and B2 (Scheme 3).
The Ir-containing complex with the 1,1-diphenyl-3-butenyl
ligand does not undergo ꢇ-hydrogen elimination because the
Ir–C bond is too stable to be cleaved by such a concerted re-
action. Once formed via cleavage of the C–C bond which is
more easily activated than the other C–C bond in the molecule,
complex B2 is converted into B1 via ꢄ-hydrogen elimination.
Although the formation of three-membered ring is thermody-
namically unfavorable, the complex having ꢂ-coordinated
methylenecyclopropane is stabilized by strong coordination
of the C=C double bond of the strained molecules. Similar
repetition of ring-opening and formation of these type
molecules by transition metal complexes was already reported.
Initial orthometalation of the phenyl group forms an inter-
mediate five-membered metallacycle with the hydrido ligand.
Reductive elimination giving a methyl group at the ligand
results in the 2-(1-methylallyl)phenyl ligand.
In summary, the reactions of 2-phenyl-1-methylenecyclo-
propane and of 2,2-diaryl-1-methylenecyclopropane with hy-
drido complexes of Rh and Ir causes C–C bond cleavage of
the three-membered ring. The bond cleavage occurs via ꢇ-al-
kyl elimination of the cyclopropylmethyl-metal intermediate.
Sterically less hindered C–C bond is activated more easily,
but the relative facility of the subsequent reaction of the inter-
mediates changes relative amounts of the final products after
isomerization.
H
H
C1
C1
H
H
H
C2
C3
H
C2
C4
H
H
H
C1
H
C2
Ph
Ph
Ph
Ph
C3
H
LnM
LnM
C4
C4
C3
Ph Ph
LnM
H
H
H
H
B1
B2
Scheme 3.
H
C1
H
H(D)
LnIr
C2
C4
H
H
H
C1
H
H
C2
C3
H
C1 C2
H
C4
H
H
LnIr
H
H
C3
Ph H
+
C3
LnIr
H
C4
Ph
Ph
H
H
L = PPh3, CO
D1
D2
H
C1
H
C1
H
H
H
C2
C3
H
C2
C3
H
H
C2
H
C4
H
∆
∆
H
H
C4
LnIr
+
C1
C3
Ph
H
LnIr
H
C4
Ph
H
H
H
H
H
D1
E
LnIr
H
+
H
C1
H
C2
H
C3
C2
C4
H
H
H
+
LnIr
C1
H
C4
H
Ph
LnIr
H
C3
H
Ph
H
D2
Scheme 4.

1476 Bull. Chem. Soc. Jpn., 78, No. 8 (2005)
C–C Bond Activation by Rh and Ir
H
C1
H
H
C1
H
C2
C3
H
H
C2
H
H
C2
H
X
H
X
C3
LnM
C1
H
C3
C4
LnM
LnM
C4
Ph
H
C4
H
X
H
H
H
H
(X = H, Ph)
Scheme 5.
methylenecyclopropane (285 mg, 2.2 mmol) at room temperature.
Stirring the solution at 50 ꢁC caused the change of the solution
from pale yellow to dark yellow. After 24 h the volatiles were
removed under reduced pressure. Addition of 10 cm3 of hexane
to the yellow oily residue at ꢂ78 ꢁC led to the formation of a pale
yellow solid, which was washed with 10 cm3 of hexane (4 times),
collected by filtration, and dried in vacuo to give a pale yellow
powder of [Ir{ꢀ2-(o-C6H4)CH(Me)CH=CH2-ꢁC1}(CO)(PPh3)2]
(2) (91 mg, 0.11 mmol, 47%). NMR yield of 2 was 82%. Complex
2 crystallizes from toluene–hexane at ꢂ20 ꢁC as colorless crystals.
Experimental
General. All manipulations of the complexes were carried
out using standard Schlenk techniques under an argon or a nitro-
gen atmosphere. THF and toluene grade were distilled from
sodium and benzophenone prior to use or were purchased from
Kanto Chemicals Co., Ltd. [RhH(CO)(PPh3)3],53,54 [IrH(CO)-
(PPh3)3],75,76 2-phenyl-1-methylenecyclopropane, 2,2-diphenyl-
1-methylenecyclopropane, and 2,2-bis(4-fluorophenyl)-1-methyl-
enecyclopropane,77 1-phenyl-1,3-butadiene, 2-phenyl-1,3-buta-
diene, and 1,1-diphenyl-1,3-butadiene,78,79 were prepared accord-
ing to the literature methods.
ꢁ
1H NMR (300 MHz, benzene-d6, 25 C): ꢃ 1.53 (d, J ¼ 6:6 Hz,
3H, Me), 1.79 (m, 1H), 2.85 (m, 2H), 3.48 (m, 1H), 6.35–7.62
(m, 34H, Ph). 31P{1H} NMR (121.5 MHz, CD2Cl2, 25 ꢁC): ꢃ
0.36 and 3.31 (d, JðP{PÞ ¼ 43:4 Hz, major), 1.66 and 4.28 (d,
JðP{PÞ ¼ 40:1 Hz, minor). 13C{1H} NMR (75.3 MHz, CD2Cl2,
25 ꢁC): ꢃ 23.5 (d, JðC{PÞ ¼ 8:1 Hz, Me), 28.1 (dd, JðC{PÞ ¼
27:0, JðC{PÞ ¼ 6:9 Hz), 44.4 (s), 55.3 (dd, JðC{PÞ ¼ 25:3,
JðC{PÞ ¼ 4:6 Hz), 122.5 (d, JðC{PÞ ¼ 3:1 Hz, Ph), 124.5 (t,
JðC{PÞ ¼ 2:5 Hz, Ph), 124.7 (d, JðC{PÞ ¼ 1:3 Hz, Ph), 127.8
(d, JðC{PÞ ¼ 9:2 Hz, PPh3-ortho), 128.0 (d, JðC{PÞ ¼ 9:2 Hz,
PPh3-ortho), 129.5 (d, JðC{PÞ ¼ 1:7 Hz, PPh3-para), 129.6
(d, JðC{PÞ ¼ 1:7 Hz, PPh3-para), 134.1 (d, JðC{PÞ ¼ 10:9
Hz, PPh3-meta), 134.2 (d, JðC{PÞ ¼ 11:4 Hz, PPh3-meta), 136.5
(dd, JðC{PÞ ¼ 40:2, JðC{PÞ ¼ 2:3 Hz, PPh3-ipso), 137.5 (dd,
JðC{PÞ ¼ 37:4, JðC{PÞ ¼ 2:3 Hz, PPh3-ipso), 141.2 (dd,
JðC{PÞ ¼ 11:8, JðC{PÞ ¼ 3:2 Hz), 150.1 (dd, JðC{PÞ ¼ 12:2,
JðC{PÞ ¼ 9:0 Hz), 154.2 (dd, JðC{PÞ ¼ 5:2, JðC{PÞ ¼ 2:5 Hz),
179.6 (dd, JðC{PÞ ¼ 8:6, JðC{PÞ ¼ 5:2 Hz, CO). IR (KBr):
1977 cmꢂ1, ꢅ(CO). Anal. calcd for C47H41OP2Ir: C, 64.44; H,
4.72%. Found: C, 64.85; H, 4.70%.
NMR spectra (1H, 13C{1H}, and 31P{1H}) were recorded on
JEOL EX-400 and Varian Mercury 300 spectrometers. The
1H NMR peak positions were referenced with the residual peak
of the solvent, while the 13C{1H} NMR peak positions were deter-
mined by using the solvent signals as the reference. An external
standard (85% H3PO4, ꢃ 0) was used in the 31P{1H} NMR mea-
surement. The IR spectra were recorded on a Shimadzu FTIR-
8100A spectrometer in KBr. Elemental analyses were carried
out with a Yanaco MT-5 CHN autocorder.
Reaction of 2-Phenyl-1-methylenecyclopropane with [IrH-
(CO)(PPh3)3] at Room Temperature. To a solution of [IrH-
(CO)(PPh3)3] (223 mg, 0.22 mmol) in 10 cm3 of toluene was
added 2-phenyl-1-methylenecyclopropane (0.074 cm3, 0.54
mmol) at room temperature. After 24 h the solvent was removed
by evaporation. Addition of hexane (10 cm3) to the yellow oily
substance led to the formation of a pale yellow solid, which was
washed with 10 cm3 of hexane (4 times), collected by filtration,
and dried in vacuo to give [Ir{ꢀ2-CH2CH(Ph)CH=CH2-ꢁC1}-
(CO)(PPh3)2] (1) as a colorless solid (171 mg, 0.20 mmol,
88%). Recrystallization from toluene at ꢂ20 ꢁC gave colorless
crystals. 1H NMR (300 MHz, benzene-d6, 25 ꢁC): ꢃ 0.11 (m,
1H), ca. 1.70 (overlapped m, 2H), 1.81 (m, 1H), 2.96 (m, 1H),
4.48 (m, 1H), 6.85–7.73 (m, 35H, Ph). 31P{1H} NMR (121.5
MHz, CD2Cl2, 25 ꢁC): ꢃ ꢂ4:93 (d, JðP{PÞ ¼ 8:9 Hz), 8.14 (d,
JðP{PÞ ¼ 8:9 Hz). 13C{1H} NMR (75.3 MHz, CD2Cl2, 25 ꢁC):
ꢃ ꢂ12:4 (d, J ¼ 63:2 Hz), 28.2 (dd, JðC{PÞ ¼ 20:9, JðC{PÞ ¼
14:8 Hz), 31.2 (dd, JðC{PÞ ¼ 7:9 Hz, JðC{PÞ ¼ 2:8 Hz), 51.8
(brs), 125.3 (Ph), 125.7 (Ph), 127.7 (Ph), 127.9 (d, JðC{PÞ ¼ 9:2
Hz, PPh3-ortho), 127.9 (d, JðC{PÞ ¼ 9:2 Hz, PPh3-ortho), 129.3
(d, JðC{PÞ ¼ 1:5 Hz, PPh3-para), 129.8 (d, JðC{PÞ ¼ 1:7 Hz,
PPh3-para), 133.7 (d, JðC{PÞ ¼ 10:9 Hz, PPh3-meta), 134.3 (dd,
JðC{PÞ ¼ 34:9, JðC{PÞ ¼ 2:4 Hz, PPh3-ipso), 134.5 (d, JðC{PÞ ¼
11:4 Hz, PPh3-meta), 136.8 (dd, JðC{PÞ ¼ 36:5, JðC{PÞ ¼ 2:3
Hz, PPh3-ipso), 155.3 (dd, JðC{PÞ ¼ 6:9, JðC{PÞ ¼ 6:3 Hz, C6),
185.8 (dd, JðC{PÞ ¼ 16:4, JðC{PÞ ¼ 7:1 Hz, CO). IR (KBr):
1939 cmꢂ1, ꢅ(CO). Anal. calcd for C47H41OP2Ir: C, 64.44; H,
4.72%. Found: C, 64.60; H, 4.72%.
NMR Experiment for the Reaction of 2-Phenyl-1-methyl-
ꢀ
enecyclopropane with [IrH(CO)(PPh3)3] at 50 C. To a solu-
tion of [IrH(CO)(PPh3)3] (20 mg, 0.020 mmol) in 0.6 cm3 of ben-
zene-d6 was added 2-phenyl-1-methylenecyclopropane (0.027
cm3, 0.20 mmol) at room temperature. The mixture was heated
at 50 ꢁC and the 1H NMR spectrum after 40 h revealed formation
of 2 (82%), 2-phenyl-1,3-butadiene (470% based on Ir), and 1-
phenyl-1,3-butadiene (177% based on Ir).
Reaction of 2,2-Diphenyl-1-methylenecyclopropane with
[IrH(CO)(PPh3)3] at 50 ꢀC. To a solution of [IrH(CO)(PPh3)3]
(223 mg, 0.22 mmol) in 10 cm3 of toluene was added 2,2-diphen-
yl-1-methylenecyclopropane (0.134 cm3, 0.54 mmol) at ambient
temperature. The reaction mixture was heated to 50 ꢁC and stirred
for 15 h. The resulting pale yellow solution was subjected to evap-
oration to give yellow oily substances, which were washed with
10 cm3 of hexane (4 times). The complete removal of hexane fur-
nished [Ir{ꢀ2-CH2CPh2CH=CH2-ꢁC1}(CO)(PPh3)2] (3) (164
mg, 0.17 mmol, 78%) as a white powder. Recrystallization from
toluene–hexane gave colorless prismatic crystals. 1H NMR (300
ꢁ
Reaction of 2-Phenyl-1-methylenecyclopropane with [IrH-
(CO)(PPh3)3] at 50 ꢀC. To a toluene (10 cm3) solution of
[IrH(CO)(PPh3)3] (222 mg, 0.22 mmol) was added 2-phenyl-1-
MHz, benzene-d6, 25 C): ꢃ ꢂ0:70 (ddd, J ¼ 13:5, 8.4, 4.8 Hz,
1H, Ir–CH2), 1.63 (m, 1H), 1.75 (m, 1H), 1.93 (dd, J ¼ 8:4, 3.3
Hz, 1H), 3.00 (m, 1H), 6.79–7.84 (m, 40H, Ph). 31P{1H} NMR

Y. Nishihara et al.
Bull. Chem. Soc. Jpn., 78, No. 8 (2005) 1477
(121.5 MHz, CD2Cl2, 25 ꢁC): ꢃ ꢂ4:38 (d, JðP{PÞ ¼ 6:7 Hz), 6.78
(d, JðP{PÞ ¼ 6:7 Hz). 13C{1H} NMR (75.3 MHz, CD2Cl2, 25 ꢁC):
ꢃ ꢂ7:0 (d, JðC{PÞ ¼ 62:0 Hz), 30.8 (dd, JðC{PÞ ¼ 8:3, JðC{PÞ ¼
2:6 Hz), 32.9 (d, JðC{PÞ ¼ 25:3 Hz), 61.4 (d, JðC{PÞ ¼ 1:7 Hz),
124.6 (Ph-para), 125.2 (Ph-para), 125.3 (Ph-ortho), 125.6 (Ph-ip-
so), 127.1 (Ph-ortho), 127.6 (Ph-meta), 127.9 (Ph-meta), 127.9 (d,
JðC{PÞ ¼ 9:2 Hz, PPh3-ortho), 128.1 (d, JðC{PÞ ¼ 9:2 Hz, PPh3-
ortho), 128.5 (Ph-ipso), 129.3 (d, JðC{PÞ ¼ 1:7 Hz, PPh3-para),
129.8 (d, JðC{PÞ ¼ 2:3 Hz, PPh3-para), 133.7 (d, JðC{PÞ ¼
10:9 Hz, PPh3-meta), 134.0 (dd, JðC{PÞ ¼ 41:9, JðC{PÞ ¼ 2:3
Hz, PPh3-ipso), 134.5 (d, JðC{PÞ ¼ 11:5 Hz, PPh3-meta), 136.7
(dd, JðC{PÞ ¼ 37:3, JðC{PÞ ¼ 2:3 Hz, PPh3-ipso), 184.9 (dd,
J ¼ 14:4, 7.5 Hz, CO). IR (KBr): 1945 cmꢂ1, ꢅ(CO). Anal. calcd
for C53H45OP2Ir: C, 66.86; H, 4.76%. Found: C, 66.43; H, 5.15%.
Reaction of 2,2-Diphenyl-1-methylenecyclopropane with
[IrH(CO)(PPh3)3] at 100 ꢀC. To a solution of [IrH(CO)(PPh3)3]
(223 mg, 0.22 mmol) in 10 cm3 of toluene was added 2,2-diphen-
yl-1-methylenecyclopropane (0.134 cm3, 0.54 mmol). Heating of
ꢃ 6.1 (dd, JðRh{CÞ ¼ 66 Hz, JðC{PÞ ¼ 12 Hz), 48.3 (s), 51.0
(dd, JðRh{CÞ ¼ 21 Hz, JðC{PÞ ¼ 5 Hz), 59.0 (t, J ¼ 3 Hz),
124.7 (Ph), 125.7 (Ph), 125.7 (Ph), 127.1 (Ph), 127.9–128.3
(PPh3-ortho), 128.8–129.1 (PPh3-para), 133.6–134.5 (PPh3-
meta), 135.2 (d, JðC{PÞ ¼ 31:0 Hz, PPh3-ipso), 137.3 (d,
JðC{PÞ ¼ 24:7 Hz, PPh3-ipso), 150.6 (Ph), 157.6 (Ph), 201.2
(ddd, J(Rh–C)=71 Hz, JðC{PÞ ¼ 16 Hz, JðC{PÞ ¼ 12 Hz, CO).
IR (KBr): 1952 cmꢂ1, ꢅ(CO). Anal. calcd for C53H45OP2Rh: C,
73.78; H, 5.26%. Found: C, 73.58; H, 5.72%.
The reaction of 2,2-di(4-fluorophenyl)-1-methylenecyclopro-
pane was carried out in an NMR sample scale as follows. To a
benzene-d6 (0.6 cm3) solution of [RhH(CO)(PPh3)3] (18.4 mg,
0.020 mmol) in an NMR tube was added 2,2-di(4-fluorophenyl)-
1-methylenecyclopropane (0.0058 cm3, 0.024 mmol) at room tem-
perature. The initial orange solution was immediately turned into
red. Monitoring the reaction by 1H NMR revealed formation of
[Rh{ꢀ2-CH2C(C6H4-F-4)2CH=CH2-ꢁC1}(CO)(PPh3)2] (5b) in
1
93% yield. H NMR (300 MHz, benzene-d6, 25 ꢁC): ꢃ 0.37 (m,
ꢁ
the resulting mixture at 100 C for 48 h furnished a pale yellow
1H), 1.61 (s, 1H), 2.19 (t, J ¼ 7 Hz, 1H), 2.24 (t, J ¼ 10 Hz,
1H), 3.16 (m, 1H), 6.64 (t, J ¼ 8 Hz, 2H), 6.87–7.02 (m, 24H, ar-
omatics), 7.32–7.45 (m, 12H, aromatics). 31P{1H} NMR (121.5
MHz, benzene-d6, 25 ꢁC): ꢃ 38.1 (dd, JðRh{PÞ ¼ 90 Hz, JðP{PÞ ¼
19 Hz), 26.7 (dd, JðRh{PÞ ¼ 121 Hz, JðP{PÞ ¼ 19 Hz). IR (KBr):
1954 cmꢂ1, ꢅ(CO). Isomerization of 5b into 6b at room temper-
ature in solution prevented 13C{1H} NMR measurement of 5b.
Reaction of 2,2-Diphenyl-1-methylenecyclopropane with
[RhD(CO)(PPh3-d15)3]. To a benzene-d6 (0.60 cm3) solution
of [RhD(CO)(PPh3-d15)3] (19 mg, 0.020 mmol) was added 2,2-di-
phenyl-1-methylenecyclopropane (0.0050 cm3, 0.025 mmol) at
room temperature. The color of the solution was immediately
turned from yellow to orange on stirring. After 1 h 1H NMR
was measured. The results reveal that the signal at ꢃ 3.43 assigned
as D attached to the ꢄ-alkenyl carbon of the 3-butenyl ligand dis-
appeared (13% integration compared to that of 6a), indicating
87% D contents, instead a broad signal at the same chemical shift
solution, which was subjected to evaporation to give yellow oily
substances. Washing with 10 cm3 of hexane (4 times) at ꢂ78
ꢁC and removal of hexane gave [Ir{ꢀ2-(o-C6H4)CMe(Ph)CH=
CH2-ꢁC1}(CO)(PPh3)2] (4) (169 mg, 0.18 mmol, 80%) as a color-
1
ꢁ
less solid. H NMR (300 MHz, CD2Cl2, 25 C): ꢃ 0.72 (m, 1H),
1.43 (m, 1H), 1.94 (s, 3H, Me), 2.73 (m, 1H), 6.13–7.68 (m,
39H, Ph). 31P{1H} NMR (121.5 MHz, CD2Cl2, 25 ꢁC): ꢃ 2.54
(d, JðP{PÞ ¼ 6:7 Hz), 4.52 (d, JðP{PÞ ¼ 6:7 Hz). 13C{1H} NMR
(75.3 MHz, CD2Cl2, 25 ꢁC): ꢃ 29.5 (d, JðC{PÞ ¼ 6:9 Hz, Me),
30.9 (d, JðC{PÞ ¼ 5:8 Hz), 57.3 (dd, JðC{PÞ ¼ 5:0, JðC{PÞ ¼
3:5 Hz), 61.9 (d, JðC{PÞ ¼ 24:7 Hz), 124.4 (d, JðC{PÞ ¼ 5:8
Hz, Ph), 125.6 (Ph), 125.7 (Ph-para), 126.5 (d, JðC{PÞ ¼ 2:9
Hz, Ph), 127.7 (Ph-ortho), 127.9 (d, JðC{PÞ ¼ 9:3 Hz, PPh3-or-
tho), 128.1 (d, JðC{PÞ ¼ 9:2 Hz, PPh3-ortho), 128.2 (Ph-meta),
129.4 (PPh3-para), 129.8 (PPh3-para), 134.3 (d, JðC{PÞ ¼ 10:3
Hz, PPh3-meta), 136.0 (d, JðC{PÞ ¼ 39:6 Hz, PPh3-ipso), 142.7
(dd, JðC{PÞ ¼ 8:1, JðC{PÞ ¼ 3:5 Hz), 153.2 (Ph-ipso), 157.2 (d,
JðC{PÞ ¼ 5:7 Hz, Ir–C), 185.4 (dd, JðC{PÞ ¼ 12:2, JðC{PÞ ¼
10:5 Hz, CO). IR (KBr): 1956 cmꢂ1, ꢅ(CO). Anal. calcd for
C53H45OP2Ir: C, 66.86; H, 4.76%. Found: C, 66.71; H, 4.87%.
Thermal Reaction of 3. A solution of 3 (14 mg, 0.015 mmol)
in toluene-d8 (0.6 cm3) was placed in an NMR tube with a Teflon
cap. The sample was heated at constant temperature in an oil bath,
2
was observed in the H NMR spectrum in benzene.
Reaction of 2,2-Diaryl-1-methylenecyclopropane with
[RhH(CO)(PPh3)3] at 50 ꢀC. To a toluene (6 cm3) solution
of [RhH(CO)(PPh3)3] (206 mg, 0.22 mmol) was added 2,2-di-
phenyl-1-methylenecyclopropane (227 mg, 1.1 mmol). During
ꢁ
the reaction at 50 C, the color of the solution changed from yel-
low to reddish orange. After 24 h the volatiles were evaporated to
dryness and the resulting oily materials were washed with hexane
repeatedly at 0 ꢁC to give [Rh{ꢀ2-(o-C6H4)CMe(Ph)CH=CH2-
ꢁC1}(CO)(PPh3)2] (6a) as a pale orange solid (100 mg, 0.12
mmol, 52%). NMR yield of 6a was 85%. Recrystallization from
CH2Cl2–hexane gave pale yellow crystals. 1H NMR (400 MHz,
benzene-d6, 25 ꢁC): ꢃ 1.87 (q, 1H, J ¼ 7:6 Hz), 2.07 (s, 3H,
Me), 2.67 (q, 1H, J ¼ 8:4 Hz), 4.13 (m, 1H), 6.50–7.44 (m,
39H, Ph). 31P{1H} NMR (121.5 MHz, benzene-d6, 25 ꢁC): major:
ꢃ 28.9 (dd, JðRh{PÞ ¼ 113:5 Hz, JðP{PÞ ¼ 15:7 Hz), 31.6 (dd,
JðRh{PÞ ¼ 78:3 Hz, JðP{PÞ ¼ 15:7 Hz), minor: ꢃ 28.4 (dd,
JðRh{PÞ ¼ 116:5, JðP{PÞ ¼ 15:7 Hz), 29.7 (dd, JðRh{PÞ ¼ 78:3,
JðP{PÞ ¼ 15:7 Hz). 13C{1H} NMR (100.4 MHz, CD2Cl2, 25
ꢁC): ꢃ 32.2 (Me), 46.5 (s), 54.4 (s), 82.1 (d, J ¼ 14:7 Hz),
122.6 (Ph), 124.1 (d, J ¼ 7:3 Hz, Ph), 128.1–128.3 (PPh3-
ortho and -para), 128.5 (Ph-ipso), 128.9 (d, J ¼ 11:0 Hz, Ph),
134.3 (PPh3-meta), 135.1 (br, PPh3-ipso), 137.0 (d, J ¼ 25:7
Hz, PPh3-ipso), 142.2 (Ph), 153.2 (s), 157.0 (s), 200.5 (ddd,
JðRh{CÞ ¼ 73:5 Hz, JðC{PÞ ¼ 25:7, 7.3 Hz, CO). IR (KBr):
1966 cmꢂ1, ꢅ(CO). Anal. calcd for C53H45OP2Rh: C, 73.78; H,
5.26%. Found: C, 73.54; H, 5.55%.
1
and the H and 31P{1H} spectra were recorded at room tempera-
ture after cooling the solution quickly. The amount of 4 formed in
the solution was monitored by the change of the peak area com-
pared to a signal of anisole (ꢃ 3.39) added as an internal standard.
Experiments were carried out at 358, 363, 368, and 373 K.
Reaction of 2,2-Diphenyl-1-methylenecyclopropane with
[RhH(CO)(PPh3)3] at Room Temperature. To a toluene (10
cm3) solution of [RhH(CO)(PPh3)3] (707 mg, 0.77 mmol) was
added 2,2-diphenyl-1-methylenecyclopropane (175 mg, 0.85
mmol) at room temperature. The color of the solution was imme-
diately turned from yellow to orange on stirring. After 1 h the vol-
atiles were removed under reduced pressure. The resulting oily
materials were washed with hexane repeatedly to give [Rh{ꢀ2-
CH2CPh2CH=CH2-ꢁC1}(CO)(PPh3)2] (5a) as a pale yellow solid
1
(500 mg, 0.58 mmol, 75%). H NMR (400 MHz, benzene-d6, 25
ꢁC): ꢃ 0.52 (m, 1H), 1.87 (s, 1H), 2.20 (t, J ¼ 7 Hz, 1H), 2.36
(t, J ¼ 9 Hz, 1H), 3.43 (m, 1H), 6.80–7.75 (m, 40H, Ph).
31P{1H} NMR (160 MHz, benzene-d6, 25 ꢁC): ꢃ 38.1 (dd,
JðRh{PÞ ¼ 90 Hz, JðP{PÞ ¼ 16 Hz), 27.3 (dd, JðRh{PÞ ¼ 121
ꢁ
Hz, JðP{PÞ ¼ 16 Hz). 13C{1H} NMR (75 MHz, CD2Cl2, 25 C):

1478 Bull. Chem. Soc. Jpn., 78, No. 8 (2005)
C–C Bond Activation by Rh and Ir
[Rh{ꢀ2-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-ꢁC1}(CO)-
(PPh3)2] (6b) was prepared in 95% yield (211 mg, 0.24 mmol) by
a similar reaction of 2,2-di(4-fluorophenyl)-1-methylenecyclo-
propane (0.179 cm3, 0.74 mmol) with [RhH(CO)(PPh3)3] (227
mg, 0.25 mmol) at 50 ꢁC. Recrystallization of from CH2Cl2–
hexane gave pale yellow crystals suitable for X-ray analysis
(6b CH2Cl2 H2O). 1H NMR (400 MHz, benzene-d6, 25 ꢁC): ꢃ
1.87 (dd, 1H, J ¼ 15, 7 Hz), 1.90 (s, 3H, Me), 2.53 (dd, 1H,
J ¼ 17, 8 Hz), 3.99 (s, 1H). 31P{1H} NMR (162 MHz, benzene-
d6, 25 ꢁC): ꢃ 28.8 (dd, JðRh{PÞ ¼ 113 Hz, JðP{PÞ ¼ 16 Hz),
31.8 (dd, JðRh{PÞ ¼ 74 Hz, JðP{PÞ ¼ 16 Hz). IR (KBr): 1968
cmꢂ1, ꢅ(CO). Anal. calcd for C53H43F2OP2Rh: C, 70.83; H,
4.82%. Found: C, 70.59; H, 5.21%.
CH2), 68.7 (dddd, JðRh{CÞ ¼ 40 Hz, JðC{PÞ ¼ 12 Hz, JðC{PÞ ¼
8 Hz, JðC{PÞ ¼ 2 Hz), 125.0 (s, Ph-para), 125.2 (s, Ph-para),
127.56 (s, Ph-ortho), 127.63 (s, Ph-ortho), 128.5 (s, Ph-meta),
128.6 (s, Ph-meta), 152.8 (s, Ph-ipso), 153.0 (s, Ph-ipso). The car-
bonyl carbon was not detected due to low intensity. IR (KBr):
1638 cmꢂ1, ꢅ(CO). Anal. calcd for C26H42O10P3Rh: C, 43.96;
H, 5.96%. Found: C, 43.80; H, 6.28%.
ꢄ
ꢄ
Thermal Reaction of 5a. A benzene-d6 (0.6 cm3) solution of
5a (17 mg, 0.020 mmol) in an NMR tube was heated at 50 ꢁC. Af-
1
ter 9 h the H NMR measurement revealed that 1,1-diphenyl-1,3-
butadiene was formed in 44% yield, based on tetramethylsilane
as an internal standard. Formation of complex 8 (53%) was also
noted.
Reaction of P(OMe)3 with 5a. To a 7 cm3 of toluene solution
of 5a (180 mg, 0.21 mmol) was added P(OMe)3 (0.071 cm3, 0.60
mmol) at room temperature. After 22 h the volatiles were removed
by evaporation. Addition of hexane gave white precipitates, which
were collected by filtration to yield [Rh{ꢀ2-CO-CH2CPh2CH=
CH2-ꢁC1}(P(OMe)3)3] (7) (130 mg, 0.18 mmol, 88%). Recrystal-
lization from hexane yielded colorless crystals suitable for X-ray
analysis. 1H NMR (400 MHz, CD2Cl2, 25 ꢁC): ꢃ 2.39 (m, 1H),
2.50 (d, J ¼ 16:8 Hz, 1H), 2.67 (m, 1H), 3.20 (d, J ¼ 11:2 Hz,
9H, P(OMe)3), 3.51 (d, J ¼ 10:0 Hz, 9H, P(OMe)3), 3.59 (d, J ¼
10:8 Hz, 9H, P(OMe)3), 3.60–3.65 (overlapped, 1H), 4.56 (m,
1H), 7.05–7.09 (m, 2H, Ph), 7.16–7.22 (m, 4H, Ph), 7.31 (d, J ¼
7:6 Hz, 2H, Ph), 7.56 (d, J ¼ 7:6 Hz, 2H, Ph). 31P{1H} NMR (162
MHz, benzene-d6, 25 ꢁC): ꢃ 143.6 (ddd, JðRh{PÞ ¼ 143 Hz,
JðP{PÞ ¼ 74 Hz, JðP{PÞ ¼ 66 Hz), 147.8 (ddd, JðRh{PÞ ¼ 228
Hz, JðP{PÞ ¼ 74 Hz, JðP{PÞ ¼ 33 Hz), 152.1 (ddd, JðRh{PÞ ¼
214 Hz, JðP{PÞ ¼ 66 Hz, JðP{PÞ ¼ 33 Hz). 13C{1H} NMR
(100.4 MHz, CD2Cl2, 25 ꢁC): ꢃ 33.9 (ddt, JðRh{CÞ ¼ 34 Hz,
JðC{PÞ ¼ 9 Hz, JðC{PÞ ¼ 6 Hz, CH=CH2), 51.0 (d, JðC{PÞ ¼
2 Hz, OCH3), 51.9 (d, JðC{PÞ ¼ 6 Hz, OCH3), 52.6 (d,
JðRh{CÞ ¼ 34 Hz), 64.0 (dt, JðRh{CÞ ¼ 41 Hz, JðC{PÞ ¼ 4 Hz,
NMR Study of the Reaction of 2,2-Diphenyl-1-methylene-
cyclopropane with 4. To a benzene-d6 (0.6 cm3) solution of
5a (17.2 mg, 0.020 mmol) was added 0.040 cm3 (0.20 mmol) of
2,2-diphenyl-1-methylenecyclopropane in an NMR tube at 50
ꢁC. After 36 h the 1H NMR measurement revealed that 1,1-di-
phenyl-1,3-butadiene in 439% and 6a in 60% yield, respectively,
based on tetramethylsilane as an internal standard.
Reaction of 1,1-Diphenyl-1,3-butadiene with [RhH(CO)-
(PPh3)3] at Room Temperature. To a solution of [RhH(CO)-
(PPh3)3] (18 mg, 0.020 mmol) in 0.6 cm3 of toluene-d8 was added
1,1-diphenyl-1,3-butadiene (8.3 mg, 0.040 mmol) at room temper-
1
ature. After 24 h the H NMR spectra indicate the formation of 8
in 20% yield. 1H NMR (400 MHz, toluene-d8, 25 ꢁC): ꢃ 1.14 (dd,
3H, J ¼ 3:9 Hz, J ¼ 6:3 Hz), 2.93 (m, 1H), 5.61 (dd, 1H, J ¼ 2:0
Hz, J ¼ 12:7 Hz).
X-ray Crystallography. Single crystals of 3, 6b, and 7, suit-
able for X-ray diffraction studies, were obtained by recrystalliza-
tion and were sealed in capillary tubes under argon. Crystallo-
graphic data and details of refinement are summarized in Table 3.
Intensities were collected for Lorentz and polarization effects on
a Rigaku AFC-5R or AFC-7R automated four-cycle diffractome-
Table 3. Crystallographic Data and Details of Structure Refinement
3
C53H45OP2Ir (C7H8)2
6b
C53H45OP2F2Rh CH2Cl2 H2O
7
C26H42O10P3Rh
710.44
monoclinic
C2=c (No. 15)
18.020(3)
9.704(5)
19.332(3)
90
Formula
ꢄ
ꢄ
ꢄ
Formula weight
Crystal system
Space group
1136.39
monoclinic
C2=c (No. 15)
28.627(7)
20.053(5)
23.017(6)
90
1900.49
triclinic
ꢂ
P1 (No. 2)
ꢁ
a/A
19.556(4)
22.248(5)
11.112(2)
101.62(2)
99.51(1)
100.20(2)
4558(2)
2
ꢁ
b/A
ꢁ
c/A
ꢈ/ꢁ
ꢇ/ꢁ
ꢄ/ꢁ
122.69(2)
90
11120(5)
8
2.507
108.82(1)
90
3299(1)
4
0.733
ꢁ 3
V/A
Z
ꢉ(Mo Kꢈ)/mmꢂ1
F(000)
0.550
1952
1.385
4624
1.357
0:50 ꢃ 0:30 ꢃ 0:05
5.0–55.0
13133
1472
1.475
0:30 ꢃ 0:20 ꢃ 0:05
5.0–55.0
7793
Dc/g cmꢂ3
Crystal size/mm3
2ꢊ range/ꢁ
No. of unique reflns
No. of used reflns
No. of variables
R
0:43 ꢃ 0:25 ꢃ 0:05
5.0–55.0
16292
8187
570
0.042
0.034
1.82
10482
1079
0.061
0.074
3.18
5697
361
0.053
0.069
4.03
a)
Rw
GOF
2
a) Weighting scheme ꢆ½ðFoÞ ꢅꢂ1
.

Y. Nishihara et al.
Bull. Chem. Soc. Jpn., 78, No. 8 (2005) 1479
ꢁ
ter by using Mo Kꢈ radiation (ꢋ ¼ 0:7107 A) and !-2ꢊ scan
method, and an empirical absorption correction ( scan) was ap-
plied.
21 M. Suginome, T. Matsuda, and Y. Ito, J. Am. Chem. Soc.,
122, 11015 (2000).
22 Y. Nishihara, M. Itazaki, and K. Osakada, Tetrahedron
Lett., 43, 2059 (2002).
23 M. Itazaki, Y. Nishihara, and K. Osakada, J. Org. Chem.,
67, 6889 (2002).
24 X. Yang, A. M. Seyam, P. F. Fu, and T. J. Marks, Macro-
molecules, 27, 4625 (1994).
25 L. Jia, X. Yang, S. Yang, and T. J. Marks, J. Am. Chem.
Soc., 118, 1547 (1996).
26 Y. Luo, P. Selvam, Y. Ito, S. Takami, M. Kubo, A.
Imamura, and A. Miyamoto, Organometallics, 22, 2181 (2003).
27 K. Osakada and D. Takeuchi, Adv. Polym. Sci., 171, 137
(2004).
28 D. Takeuchi, S. Kim, and K. Osakada, Angew. Chem., Int.
Ed., 40, 2685 (2001).
29 S. Kim, D. Takeuchi, and K. Osakada, J. Am. Chem. Soc.,
124, 762 (2002).
Calculations were carried out by using a program package teXsan
for Windows. The structures were all solved by the Patterson
method. A full matrix least-square refinement was used for the
non-hydrogen atoms with anisotropic thermal parameters. All
non-hydrogen atoms were refined with anisotropic thermal
parameters, whereas all hydrogen atoms were located by assuming
the ideal geometry and included in the structure calculation with-
out further refinement of the parameters.80
Crystallographic data have been deposited at the CCDC, 12
Union Road, Cambridge CB21EZ, UK (Fax: +44 1223 336033;
e-mail: deposit@ccdc.cam.ac.uk) and copies can be obtained on
request, free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, by quoting the publication citation and the depo-
sition number 264236–264238.
30 D. Takeuchi and K. Osakada, Chem. Commun., 2002, 646.
31 D. Takeuchi, K. Anada, and K. Osakada, Macromolecules,
35, 9628 (2002).
32 D. Takeuchi, and K. Osakada, Macromolecules, 38, 1528
(2005).
This work was financially supported by a Grant-in-Aid for
Scientific Research for Young Chemists No. 13740412 and
for Scientific Research on Priority Areas, from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
´
33 P. Binger, T. R. Martin, R. Benn, A. Rufınska, and G.
Schroth, Z. Naturforsch, 39b, 993 (1984).
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