Synthesis and structure of methylpalladium(II) and -platinum(II) complexes with 2-allylphenoxido ligands, trans-PdMe(O6H4CH2CH=CH2-o)(PR3 )2 (R=Me, Ph) and PtMe(η1-O, η2-C,C-OC6H4CH2CH=CH2 -o)(PMe3).

Article abstract of DOI:10.1016/S0022-328X(97)00780-8

Reactions of cis-PdMe₂L₂ (L=PMe₃, PPh₃, 0.5 dppp [dppp=Ph₂P(CH₂)₃PPh₂]) with equimolar 2-allylphenol afford the new complexes PdMe(OC₆H₄CH₂CH=CH₂-o)L2 (1: L=PMe₃; 2: L=PPh₃; 3: L=0.5 dppp) in moderate to high yields. Addition of 2,2,2-trifluoro-1-phenylethanol to equimolar 1 results in formation of trans-PdMe(O₆H₄CH₂CH=CH₂-o)(PMe ₃)₂ · (HOCH(CF₃)Ph), (4) which has been characterized by X-ray crystallography and NMR spectroscopy. Complex 4 contains O-H...O hydrogen bonding between the allylphenoxido ligand and associated alcohol (O...O=2.635(6) A). The platinum complex PtMe(OC₆H₄CH₂CH=CH₂-o)(dppp), (5) is obtained from the alkoxido ligand exchange reaction of PtMe(OCH(CF₃)₂)(dppp) with 2-allylphenol. Similar reaction of cis-PtMe(OR)(PMe₃)₂ with equimolar 2-allylphenol at room temperature gives trans-PtMe(OC₆H₄CH₂CH=CH₂-o)(PMe₃)₂ (6) in 55% yield. In contrast, reaction of cis-PtMe(OCH(CF₃)₂)(PMe₃)₂ · (HOCH(CF₃)₂) with excess 2-allylphenol at room temperature gives a mixture of 6 and PtMe(η¹-O, η²-C,C-OC₆H₄CH₂CH=CH₂ -o)(PMe₃) (7) which are isolated in 16 and 28% yields, respectively. The isolated complex 7 has been characterized by NMR spectroscopy using several pulse techniques and X-ray analysis. The molecule has a distorted square-planar coordination around the metal center. The olefinic group in 2-allylphenoxido ligand is coordinated to the Pt center in a perpendicular fashion to the coordination plane.

Full text of DOI:10.1016/S0022-328X(97)00780-8

Journal of Organometallic Chemistry 558 (1998) 41–49
Synthesis and structure of methylpalladium(II) and -platinum(II)
complexes with 2-allylphenoxido ligands,
trans-PdMe(O6H4CH2CHꢀCH2-o)(PR3)2 (R=Me, Ph) and PtMe(p1-O,
p2-C,C-OC6H4CH2CHꢀCH2-o)(PMe3). Simple O-coordination and
chelating coordination depending on the metal center and auxiliary
phosphine ligand
Yong-Joo Kim a,*, Jae-Young Lee a, Kohtaro Osakada b
a Department of Chemistry, Kangnung National Uni6ersity, Kangnung, 210-702, South Korea
b Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226, Japan
Received 8 July 1997; received in revised form 2 December 1997
Abstract
Reactions of cis-PdMe2L2 (L=PMe3, PPh3, 0.5 dppp [dppp=Ph2P(CH2)3PPh2]) with equimolar 2-allylphenol afford the new
complexes PdMe(OC6H4CH2CHꢀCH2-o)L2 (1: L=PMe3; 2: L=PPh3; 3: L=0.5 dppp) in moderate to high yields. Addition of
2,2,2-trifluoro-1-phenylethanol to equimolar 1 results in formation of trans-PdMe(O6H4CH2CHꢀCH2-o)(PMe3)2 · (HOCH(CF3)
Ph), (4) which has been characterized by X-ray crystallography and NMR spectroscopy. Complex 4 contains O–H···O hydrogen
˚
bonding between the allylphenoxido ligand and associated alcohol (O···O=2.635(6) A). The platinum complex Pt-
Me(OC6H4CH2CHꢀCH2-o)(dppp), (5) is obtained from the alkoxido ligand exchange reaction of PtMe(OCH(CF3)2)(dppp) with
2-allylphenol. Similar reaction of cis-PtMe(OR)(PMe3)2 with equimolar 2-allylphenol at room temperature gives trans-Pt-
Me(OC6H4CH2CHꢀCH2-o)(PMe3)2 (6) in 55% yield. In contrast, reaction of cis-PtMe(OCH(CF3)2)(PMe3)2 · (HOCH(CF3)2) with
excess 2-allylphenol at room temperature gives a mixture of 6 and PtMe(p1-O, p2-C,C-OC6H4CH2CHꢀCH2-o)(PMe3) (7) which
are isolated in 16 and 28% yields, respectively. The isolated complex 7 has been characterized by NMR spectroscopy using several
pulse techniques and X-ray analysis. The molecule has a distorted square-planar coordination around the metal center. The
olefinic group in 2-allylphenoxido ligand is coordinated to the Pt center in a perpendicular fashion to the coordination plane.
© 1998 Elsevier Science S.A. All rights reserved.
Keywords: Palladium; Platinum; Phenoxide; Hydrogen bonding; Crystal structure
1. Introduction
the metal–phenoxido bond [9–11]. Most of the phe-
noxido complexes were prepared by metathesis reac-
tions of chloro complex with alkaline metal phenoxido
or by reaction of hydrido or alkyl metal species with
phenol. Previously we have reported that reactions of
dialkyl-nickel (II), -palladium (II), and -platinum(II)
complexes stabilized by tertiary or chelating phosphines
with equimolar phenols with various substituents,
HOC6H4X-p (X=H, Me, OMe, F, Cl, and Br), pro-
ceed smoothly at room temperature to give alkyl-nickel
The chemistry of late transition metal phenoxides has
been the subject of increasing attention because of their
characteristic chemical properties such as C–O bond
formation through coupling of the phenoxido and acyl
ligand [1,2], O–H···O hydrogen bonding between phe-
noxido ligand and phenol [3–8], and CO insertion into
* Corresponding author.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00780-8

42
Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
(II), -palladium (II), and -platinum (II) phenoxides or
complexes, MR(OAr)L2 · (HOAr) containing phenol
associated with phenoxido ligands through hydrogen
bonding [6]. Recently, van Koten and his coworkers [7]
also showed that reactions of dimethylpalladium(II)
complexes with auxiliary N,N or N,P-donor chelating
ligands with phenol or pare- substituted phenols lead to
the formation of palladium(II) phenoxides or those
with associated phenol through the O–H···O hydrogen-
bond stabilized by the amine ligands.
On the other hand, Pd(II) complex containing both
alkoxido and y-coordinated olefin ligands seems to be
of importance as a possible intermediate of alkoxypal-
ladation of olefins or the Wacker type reaction. A
strategy to isolate this kind of Pd complex and to
investigate its properties is to use alcohol containing
CꢀC double bond at the proper position to serve as the
anchor in the molecule as the ligand precursor. Liga-
tion of alkoxido would be accompanied by y-coordina-
tion of the CꢀC double bond. In this paper as an
extension of the previous work we will show chemistry
of methylpalladium and platinum(II) complexes con-
taining 2-allylphenoxido ligand including synthetic de-
caused by coupling with two unequivalent phosphorus
1
nuclei. The H- and 13C-NMR signals of PMe3 ligands
of 1 and 13C{1H}-NMR peak due to ipso carbons of
PPh3 ligands of 2 are observed as apparent triplets due
to virtual coupling. The 13C{1H}-NMR signals due to
olefinic carbons of 2-allylphenoxido ligand of 1–3 ap-
pear at quite similar position to each other (113.0–
114.0 and 139.1–140.0 ppm) and to the corresponding
signals of uncoordinated 2-allylphenol. The above re-
sults strongly indicate the absence of coordination or
interaction between CꢀC double bond of the 2-allylphe-
noxido ligand and the metal center.
Previously we reported that reaction of cis-
PdMe2(PMe3)2 with excess phenol gives a complex for-
mulated as trans-PdMe(OPh)(PMe3)2 · (HOPh), which
is prepared also from the reaction of trans-PdMe-
(OPh)(PMe3)2 with phenol [6]a. Strong O–H···O hydro-
gen bonding exists between the phenoxido ligand and
phenol not only in the solid state but in solution.
Reaction of cis-PdMe2(PMe3)2 with excess 2-allylphe-
nol does not produce the hydrogen-bonded complex
such as trans-PdMe(OC6H4CH2CHꢀCH2-o)(PMe3)2 ·
(HOC6H4CH2CHꢀCH2-o) but gives 1 as the sole
isolable product. The difference of the reaction prod-
ucts between phenol and 2-allylphenol is ascribed to
weakening the O–H···O hydrogen bond of the 2-al-
lylphenoxido ligand with 2-allylphenol caused by steric
congestion and/or to poor crystallinity of trans-
(C6H4CH2CHꢀCH2-o)L2 · (HOC6H4CH2CHꢀCH2-o),
preventing from its crystallization from the solution.
Complex 1 reacts with equimolar 2,2,2-trifluoro-1-
tails,
spectroscopic
characterization,
and
crystallographic results of some of the complexes.
2. Results and discussion
Reactions of cis-PdMe2L2 (L=PMe3, PPh3, 0.5
dppp) with an equimolar amount of 2 allylphenol at
0°C give trans-PdMe(OC6H4CH2CHꢀCH2-o)L2 (1: L=
PMe3; 2 L=PPh3) and PdMe(OC6H4–CH2CHꢀCH2-
o)(dppp), (3) in moderate to good yields, respectively.
phenylethanol
to
give
trans-PdMe(OC6H4-o-al-
lyl)(PMe3)2 · (HOCH(CF3)ph) (4) as shown in Eq. (2).
Complex 4 has been isolated as a colorless crystalline
solid, and characterized by X-ray crystallography and
NMR spectroscopy as shown below. The structure
L−L=Ph2P−(CH2)3−PPh2, 3
Complexes 1–3 are colorless or yellow crystalline solids
whose IR spectra give rise to a small absorption peak at
1634–1636 cm−1 due to CꢀC stretching frequency of
the allyl group. Similarity of the peak position to the
corresponding band of free 2-allylphenol suggests that
the CꢀC double bond of the allylphenoxido ligand does
having
2,2,2-trifluoro-1-phenylethanol
hydrogen
bonded to the coordinated oxygen of the 2-allylphenox-
ido ligand is stable in the solid state at room tempera-
ture but the complex readily loses the associated fluoro
alcohol in solution during recrystallization and regener-
ates complex 1.
1
not coordinate to the metal center. The H- and 13C-
Fig. 1 shows the molecular structure of 4 whose
selected bond lengths and angles are listed in Table 1.
The molecular structure of 4 contains slightly distorted
square planar coordination around the palladium cen-
ter containing two mutually bans PMe3 ligands as well
as methyl and 2-allylphenxido ligands. 2,2,2-Trifluoro-
1-phenylethanol forms an O–H···O hydrogen bonding
with the coordinated oxygen atom. The O···O non-
NMR spectra as well as results of 13C–1H COSY
measurement have provided sufficient information to
1
characterize these complexes unambiguously. The H-
and 13C{1H}-NMR signals due to the methyl ligand of
1 and 2 appear at reasonable positions accompanied by
coupling with two magnetically equivalent phosphorus
nuclei. Complex 3 having cis coordination shows the
1H- and 13C{1H}-NMR signals as a doublet of doublets
˚
bonded distance (2.635(6) A) falls in the range of the

Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
43
1
The H-NMR spectrum of 4 taken in CDCl3 (25°C)
shows an OH hydrogen peak of the associated alcohol
at 5.8 ppm which is at a higher magnetic field position
than those of other palladium phenoxides with an
associated fluoro alcohol or phenol. These results indi-
cate weak hydrogen bonding between the phenoxido
and an alcohol in solution and agree with the observa-
tion that 4 dissociates easily the fluoro alcohol in the
solution.
We have examined preparation of analogous platinu-
m(II) complexes. Similar reaction of PtMe2(dppp) with
2-allylphenol does not give the complex Pt-
Me(OC6H4CH2CHꢀCH2-o)(dppp), (5) at all. On the
basis of previous our results including reaction of cis-
PtMe(OCH(CF3)2)(PMe3)2 by phenol to give cis-Pt-
Me(OPh)(PMe3)2 [6]b, similar ligand exchange reaction
of cis-PtMe(OCH(CF3)2)(dppp) has been carried out by
use of 2-allylphenol.
The reaction proceeds smoothly to give Pt-
Me(OC6H4CH2CHꢀCH2-o)(dppp) (5) in 60% yield as a
colorless solid (Eq. (3)).
Fig. 1. ORTEP drawing of 4 showing the atomic labeling scheme and
50% probability thermal ellipsoids.
˚
hydrogen bond with significant strength (2.55–2.65 A),
and are comparable to O···O distances and angles in
related palladium(II) and platinum(II) alkoxide or phe-
noxide complexes [4–7]. D-fourier technique has re-
vealed position of the OH hydrogen which lies on the
The 1H-NMR spectrum of complex 5 shows the
signal due to Pt-CH3 hydrogen at 0.43 ppm as a
doubles of doublets flanked with 195Pt satellite signals.
˚
˚
O–O line (O–H=1.03(6) A, O···H=1.61(6) A, O···H–
˚
O=170(5)°). The Pd–O (2.129(3) A) distance is similar
to or slightly longer than those of previously reported
the Pd–O distances in related palladium phenoxide
complexes, bans PdMe(OC6H5)(PMe3)2 · (HOR) (R=
1
The H- and 13C{1H}-NMR signals due to the hydro-
gens and carbons of the allyl group appear at quite
similar positions to the corresponding signals of the Pd
complex 3. The 31P{1H}-NMR spectrum of 5 shows
two doublets which are accompanied by 195Pt satellites
in agreement with the cis configuration having unequiv-
alent phosphine ligands. The signal at 7.73 ppm with
coupling constant, J(195Pt–31P)=1546 Hz, is assigned
to the phosphorus atom at the trans position to the
methyl ligand, while the other phosphorus nuclei bans
to the 2-allylphenoxido ligand shows a much larger
coupling constant, J(195Pt–31P)=3807 Hz, similarly to
the already reported cis methylplatinum alkoxido com-
plexes, cis-PtMe(OPh)(PMe3)2 [6]b, PtMe(OMe)(dppe)
[13], and related Pt complexes [14].
Use of monodentate coordinating PMe3 as the auxil-
iary ligands have altered the products of the reaction of
the fluoroalkoxido platinum complexes with 2-allylphe-
nol. Reaction of cis-PtMe(OCH(CF3)2)(PMe3)2 with
equimolar 2-allylphenol at room temperature gives
trans-PtMe(OC6H4CH2CHꢀCH2-o)(PMe3)2, (6) in a
55% yield as shown in Eq. (4). However, similar reac-
tion of cis-PtMe(OCH(CF3)2)(PMe3)2 · (HOCH(CF3)2)
with excess 2-allylphenol at room temperature results in
formation of a mixture of 6 and Pt-Me(OC6H4CH2CH
˚
CH(CF3)Ph) (2.107(2) A), trans-PdMe(OC6H5)(PMe3)2
˚
· (HOC6H5) (2134(3) A), and trans-PdMe(OC6H5)
˚
(PMe3)2 (2.106(3) A) [6]a. Van Koten and his co-work-
ers have observed similar slight elongation of the Pd–O
bond of phenoxido complex with chelating diamine
auxiliary ligands [7]a,c. Non-bonded distance between
Pd and hydrogen bonded to C17 of the fluoro alcohol
˚
in 4 (2.73 A) falls within the expected sum of van der
Waals radii of H and 4d group metals, indicating the
presence of agostic interaction between the C–H group
and the Pd center [12].
Table 1
˚
Selected bond lengths (A) and angles (°) for 4
Pd–O(1)
O(1)–H(1)
Pd–C(1)
Pd–P(1)
Pd–P(2)
2.129(3) O(1)···O(2)
1.03(6) O(1)···H(1)
2.067(5) C(3)–C(8)
2.306(2) C(8)–C(9)
2.301(2) C(9)–C(10)
2.635(6)
1.61(6)
1.498(8)
1.465(9)
1.240(10)
Pd–O(1)–C(2)
P(1)–Pd–P(2)
C(1)–Pd–O(1)
121.5(3)
175.43(6)
176.7(2)
O(1)···H(1)–O(2)
P(1)–Pd–O(1)
P(2)–Pd–O(1)
170(5)
91.8(1)
92.5(1)

44
Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
ꢀCH2-o)(PMe3) (7) which are isolated by fractional
recrystallization of the product in the respective yields
of 16% and 28% as shown in Eq. (5).
The IR spectrum of 6 shows the presence of the
alkenyl stretching vibration (w(CꢀC)) in the phenoxido
ligand at 1636 cm−1 similarly to 1–3 (1636–1634 cm−
1), while the corresponding peak of 7 is shifted to lower
frequency region (1600 cm−1) by y-coordination to the
1
Pt center. The H spectrum of 6 at −20°C shows the
Fig. 2. ORTEP drawing of 7 showing the atomic labeling scheme and
30% probability thermal ellipsoids.
signal due to Pt–CH3 hydrogen as a triplet flanked with
195Pt satellites. The PMe3 hydrogen signal observed as
an apparent triplet due to virtual coupling is also
accompanied by 195Pt satellites. The other signals in-
cluding allyl hydrogen peaks of the 2-allylphenoxido
ligand are observed quite similarly to the bans Pd
complex 1. The 31P{1H}-NMR signal of 6 shows the
31P–195Pt coupling (2667 Hz) which is similar to the
already reported monomethyl complexes of Pt(II). In
distorted square planar coordination around the Pt
center which is bonded to a PMe3, a methyl, and a
2-allylphenoxido group whose CꢀC double bond is
coordinated to the metal center. The C2–C1 bond in
2-allylphenoxido ligand is perpendicularly coordinated
to the coordination plane with almost equal Pt–C bond
˚
distances (Pt–C1=2.13 and Pt–C2=2.16 A). The
1
˚
C2–C1 bond length of 7 is 1.32 A, which resembles to
contrast, the Pt–Me signal in H- spectrum of 7 ex-
hibits a doublet (J(PH)=3 Hz) with 195Pt satellites due
to the structure having the methyl and PMe3 ligands at
mutually cis positions. The 13C{1H}-NMR signals due
to olefinic carbons of the 2-allylphenoxido ligand are
observed at 79.2 and 97.8 ppm which are significantly
at higher magnetic field position than the correspond-
ing peaks of other Pd and Pt complexes in the present
study and those of 2-allylphenol. 195Pt satellite peaks
are clearly observed, indicating that the CꢀC double
bond is firmly y-coordinated to the metal center. The
1H NMR signals corresponding to, ꢀCH2, ꢀCH–, and
–CH2– hydrogens of the 2-allylphenoxido ligand also
shows splitting due to 195Pt–1H coupling and upfield
shift of the peak positions compared with those of 6
whose CꢀC double bond is not bonded to the Pt center.
free alkene (1.337 A) [15], and shorter than the corre-
˚
sponding CꢀC double bond of Zeise’s salt,
˚
KPtCl3(C2H4) · H2O
(1.38
˚
A)
[16]
and
of
Pt(C2H4)(PPh3)2 (1.43 A) [17]. Therefore, the weak
y-back donation of metal to olefin and vice verse
electron drift of olefin to metal is significant in 7. The
˚
Pt-methyl bond length (2.05(2) A) of 7 is shorter than
˚
those of cis-PtMe(OCH(CF3)2)(PMe3)2 (2.13(2) A) and
of cis-PtMe(OPh)(PMe3)2 (2.08(1) A)[6]b. These results
˚
suggest the CꢀC double bond has much weaker trans
influence than PMe3 ligand.
Table 2
˚
Selected bond lengths (A) and angles (°) for 7
Assignment of these H and 13C signals are confirmed
1
Pt–O
Pt–C(10)
Pt–P
Pt–C(1)
Pt–C(2)
P–Pt–C(1)
P–Pt–C(10)
O–Pt–C(1)
O–Pt–P
2.05(2)
1.91(4)
2.211(9)
2.13(5)
2.16(4)
95.1(10)
86.8(9)
90(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
O–C(5)
P–Pt–C(2)
P–Pt–0(1)
O–Pt–C(2)
O–Pt–C(10)
1.32(4)
1.50(4)
1.54(4)
1.35(4)
1.32(4)
98.2(8)
172.1(7)
89(1)
with the aid of 13C–1H COSY measurement and the
13C-NMR spectrum obtained in a gated decoupled
mode. In order to obtain more precise structural infor-
mation we have undertaken the study on the crystal
structure.
A suitable crystal of 7 for X-ray analysis was ob-
tained by recrystallization from a THF hexane mixture.
Fig. 2 shows the molecular structure with the atomic
numbering scheme. Selected data of bond lengths and
angles are listed in Table 2. The molecule has slightly
172.1(7)
86(1)
C(1)–Pt–C(10)
Pt–C(2)–C(1)
Pt–C(2)–C(3)
163(1)
70(2)
108(2)
C(2)–Pt–C(10)
Pt–C(1)–C(2)
Pt–0(1)–C(5)
159(1)
73(2)
128(2)

Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
45
In order to obtain more detailed insight for forma-
tion of 7 in the reaction (5) we have examined the
reaction of isolated complex 6 with excess 2-allylphenol
but observed complete recovery of the starting material.
Warming a CDCl3 solution of 6 at −20°C to room
temperature leads to partial conversion of the complex
into cis-isomer and ensuing formation of uncharacter-
ized complexes in trace amounts. These results exclude
a simple pathway from 6 to 7 involving the cis isomer
of 6 as the intermediate. However, reaction of cis-Pt-
Me(OCH(CF3)2)(PEt3)2 with 2-allylphenol results in the
sole formation of cis-PtMe(OC6H4CH2CHꢀCH2-
o)(PEt3)2 (8) which is isolated in 48% yield. At present
formation mechanism of 7 in the reaction system is not
clarified.
recorded on a Hitachi 270-30 spectrophotometer. NMR
(1H, 13C{1H} and 31P{1H}) spectra were obtained on
JEOLFX-100, GX-270 and Braker 500 MHz spectrom-
eters. Chemical shifts were referred to internal Me4Si or
to external 85% H3PO4.
PdMe2(dppp) was obtained from ligand substitution
reaction of PdMe2(tmeda) [21] with equimolar dppp
(90%). 1H-NMR(200 MHz, CDCl3, 6): 0.16(bd, 6H,
CH3), 1.85 (m, 2H, –CH2), 2.4 (m, 4H, P–CH2), 7.4–
7.7 (m, 20H, aromatic). 31P-NMR (40 MHz, CDCl3, b):
6.3 (s). Anal. Calcd for C29H32P2Pd: C, 63.46; H, 5.88.
Found: C, 63.31; H, 5.74.
3.2. Preparation of trans-PdMe(OC6H4CH2CHꢀ
CH2-o)L2 (1: L=PMe3; 2: L=PPh3; 3 L=0.5dppp)
In summary, the attempts to synthesize methylpalla-
dium(II) or -platinum(II) complexes with 2-allylphenox-
ido ligands provided the complexes whose
allylphenoxido group is bonded in a simple O-bonded
fashion. These complexes do not show coordination or
interaction of the CꢀC double bond of the ligand to the
fifth coordination site of the metal center. Ligand ex-
change reaction of the methylplatinum fluoroalkoxido
complex by 2-allylphenol resulted in formation of the
square-planar complex as one of the products, which
possesses the phenoxido ligand containing CꢀC double
bond y-coordinated to the metal center. The bond
parameters of the olefinic group bonded to the Pt
center suggests back donation in almost negligible de-
gree. Chelating complexation of the 2-allylphenoxido
ligand in 7 despite selective formation of simple O-co-
ordinated phenoxides in the reactions of dimethylpalla-
dium complexes can be partly attributed to more labile
Pd–PMe3 bond than the Pt–PMe3 bond.
To an Et2O (10 ml) solution of cis-PdMe2(PMe3)2
(562 mg, 1.95 mmol) was added 2-allylphenol (309 mg,
2.30 mmol) at 0°C. After stirring the reaction mixture
for 6 h the solvent was reduced under vacuum to cause
separation of colorless crystals, which were recrystal-
lized from ether to give 1 (475 mg, 62%). IR (KBr):
1
1636 cm−1 (w(CꢀC)). H-NMR (CDCl3, 500 MHz, l):
0.02 (t, 3H, J=7 Hz, Pd–CH3), 1.25 (t, 18H, J=3 Hz,
P(CH3)3), 3.37 (d, 2H, J=5 Hz, –CH2CHꢀCH2), 4.97
(dd, 1H, J=10, 2 Hz, –CH2CHꢀCH2), 5.02 (dd, 1H,
J=17.2 Hz, –CH2CHꢀCH2), 6.07 (m, 1H,
–
CH2CHꢀCH2), 6.4 (m, 1H, aromatic), 6.93 (m, 2H,
aromatic), 7.05 (m, 1H, aromatic). 13C{1H} NMR (125
MHz, CDCl3, l): −12.7 (t, J=7 Hz, Pd–CH3), 13.1
(t, P(CH3)3), 35.1 (–CH2CHꢀCH2), 114.0 (–
CH2CHꢀCH2), 139.1 (–CH2CHꢀCH2), 111.5, 118.5,
126.7, 128.4, 129.2, 167.9 (aromatic). 31P{1H}-NMR
(200 MHz, CDCl3, l): −13.5 (s). Anal. Calcd for
C16H30OP2Pd: C, 47.24; H, 7.43. Found: C, 47.30;
H,7.51.
3. Experimental
trans-PdMe(OC6H4CH2CHꢀCH2-o)(PPh3)2, (2) and
PdMe(OC6H4CH2CHꢀCH2-o)(dppp), (3) were similarly
obtained in 85 and 86% yields. Complex 2. IR (KBr):
3.1. General, materials, and measurement
1
1634 cm−1 (w(CꢀC)). H-NMR (CDCl3, 500 MHz, 6):
All manipulations of air-sensitive compounds were
performed under N2 or argon atmosphere with use of
standard Schlenk technique. Solvents were distilled
from Nabenzophenone. dppp (1,3-bis(diphenylphos-
phino)propane), PMe3, PPh3, 2-allylphenol, 2,2,2-trifl-
uoro-1-phenylethanol, and 1,1,1,3,3,3-hexafluoro-2-
propanol were purchased from Aldrich and used with-
out further purification. cis-PdMe2L2 (L=PMe3, PPh3)
[18,19], cis-PtMe(OCH(CF3)2)(PMe3)2 [6]b, cis-Pt-
Me(OCH(CF3)2)(PMe3)2 · (HOCH(CF3)2 [6]b, and Pt-
Me(OCH(CF3)2)(dppp) [20] were prepared by the
literature methods.
0.07 (bs, 3H, Pd–CH3), 2.80 (d, 2H, J=5 Hz, –
CH2CHꢀCH2), 4.85 (m, 2H, –CH2CHꢀCH2), 5.77 (m,
1H, –CH2CHꢀCH2), 6.08–7.76 (m, aromatic).
13C{1H}-NMR (125 MHz, CDCl3, l): −1.92 (s, Pd–
CH3), 35.1 (–CH2CHꢀCH2), 113.2 (–CH2CHꢀCH2),
139.5 (–CH2CHꢀCH2), 110.6, 119.4, 125.6, 126.8,
128.1, 129.9. 130.3, 131.4, 134.6, 166.5 (aromatic).
31P{1H}-NMR (200 MHz, CDCl3, l): 26.8 (s). Anal.
Calcd for C46H42OP2Pd: C, 70.91; H, 5.43. Found: C,
71.34; H, 5.56.
Complex 3. IR (KBr): 1634 cm−1 (w(CꢀC)). 1H-
NMR (CDCl3, 500 MHz, l): 0.32 (dd, 3H, J=3, 8 Hz,
Pd–CH3), 1.86 (m, 2H, P–CH2), 2.43 (m, 4H, P–CH2),
3.03 (d, 2H, J=5 Hz, –CH2CHꢀCH2), 4.80 (dd, 1H,
Elemental analyses were carried out by the analytical
laboratory, Tokyo Institute of Technology in Japan
and Basic Science Institute of Korea. IR spectra were

46
Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
J(PtH)=54 Hz, Pt–CH3), 1.91 (m, 2H, P–CH2), 2.48–
2.55 (m, 4H, P–CH2), 2.98 (d, 2H, J=7 Hz, –
CH2CHꢀCH2), 4.85 (dd, 1H, J=11.2 Hz,
J=10.2 Hz, –CH2CHꢀCH2), 4.89 (dd, 1H, J=17.2
Hz, –CH2CHꢀCH2), 5.86 (m, 1H, –CH2CHꢀCH2),
6.23 (m, 1H, aromatic), 6.77 (m, 2H, aromatic), 7.14–
7.96 (m, 1H, aromatic). 13C{1H}-NMR (125 MHz,
CDCl3, l): 14.2 (dd, J=3.97 Hz, Pd–CH3), 19.2 (d,
J=6, P–CH2), 27.2 (dd, J=2.19 Hz, Pd–CH2), 29.4
(dd, J=8.30 Hz, P–CH2), 35.7 (–CH2CHꢀCH2), 113.0
(–CH2CHꢀCH2), 140.0 (–CH2CHꢀCH2). 31P{1H}-
NMR (200 MHz, CDCl3, l): −6.85, 26.3 (d, J=47).
Anal. Calcd for C37H38OP2Pd: C, 66.62; H, 5.74.
Found: C, 66.95; H, 5.51.
–CH2CHꢀCH2), 4.89 (dd, 1H, J=17.1 Hz,
–
CH2CHꢀCH2), 5.77 (m, 1H, –CH2CHꢀCH2), 6.36 (m,
aromatic), 6.78–7.69 (m, aromatic). 13C{1H}-NMR
(125 MHz, CDCl3, l): 10.2 (dd, J=6.92 Hz, Pt–CH3),
19.6 (d, J=2 Hz, P–CH2), 26.7 (d, J=27 Hz, Pd–
CH2), 28.0 (dd, J=6.40 Hz, P–CH2), 34.9 (–
CH2CHꢀCH2),
113.6
(–CH2CHꢀCH2),
139.3
(–CH2CHꢀCH2). 31P{1H}-NMR (200 MHz, CDCl3,
l): 0.06, 7.73 (d, J=20 Hz, J(PtP)=3807, 1546 Hz).
Anal. Calcd for C37H38OP2Pt: C, 58.80; H, 5.07.
Found: C, 58.63; H, 4.89.
3.3. Preparation of trans-PdMe(OC6H4CH2CH
ꢀCH2-o)(PMe3)2 · (HOCH(CF3)Ph) (4)
To an Et2O (4 ml) solution of trans-
PdMe(OC6H4CH2CHꢀCH2-o)(PMe3)2 (285 mg, 0.70
mmol) was added 2,2,2-trifluoro-1-phenylethanol (142
mg, 0.81 mmol) at room temperature. After stirring the
reaction mixture for 2 h the solvent was evaporated to
dryness to leave a pasty material. Addition of hexane (5
ml) and ensuing storage of the resulting solution
overnight at −20°C caused separation of 4 as a color-
less crystals which were collected by filtration, washed
with hexane, and dried in vacuo (338 mg, 83%). IR
(KBr): 1636 cm−1 (w(CꢀC)). 1H-NMR (CDCl3, 500
MHz, l): 0.08 (t, 3H, J=7 Hz, Pd–CH3), 1.20 (t, 18H,
3.5. Preparation of trans-PtMe(OC6H4CH2CH
ꢀCH2-o)(PMe3)2, (6) and PtMe(OC6H4CH2CH
ꢀCH2-o)(PMe3), (7)
To an Et2O (5 ml) solution of cis-Pt-
Me(OCH(CF3)2)(PMe3)2 (264 mg, 0.499 mmol) was
added 2-allylphenol (80 mg, 0.598 mmol) at room
temperature. Stirring the reaction mixture for 4 h
caused separation of a white solid which was filtered,
washed with hexane, and dried in vacuo to give 6 (136
1
mg, 55%). IR (KBr): 1636 cm−1 (w(CꢀC)). H-NMR
(CDCl3, 500 MHz, l): 0.27 (t, 3H, J=7 Hz, J(PtH)=
79 Hz, Pt–CH3), 1.33 (t, 18H, J=3 Hz, J(PtH)=27
Hz, P(CH3)3), 3.35 (d, 2H, J=5 Hz, –CH2CHꢀCH2),
4.98 (dd, 1H, J=10.2 Hz, –CH2CHꢀCH2), 5.02 (dd,
1H, J=17.2 Hz, –CH2CHꢀCH2), 6.07 (m, 1H, –
CH2CHꢀCH2), 6.43 (m, 1H, aromatic), 6.98 (m, 2H,
aromatic), 7.33 (m, 1H, aromatic). 13C{1H}-NMR (125
MHz, CDCl3, l): −29.9 (t, J=6 Hz, Pt–CH3), 12.2
(t, J=18 Hz, P(CH3)3), 35.6 (s, –CH2CHꢀCH2), 113.7
(–CH2CHꢀCH2), 139.2 (–CH2CHꢀCH2), 111.8, 117.5,
126.6, 128.4, 129.3, 168.0 (aromatic). 31P{1H}-NMR
(200 MHz, CDCl3, l): −7.79 (s, J(PtP)=2667 Hz).
Anal Calcd for C16H30OP2Pt: C, 38.79; H, 6.10. Found
C, 38.49; H, 6.25.
To an ether solution (10 ml) containing cis-Pt-
Me(OR)(PMe3)2 · (HOR) (R=CH(CF3)2) (0.703 g,
1.01 mmol) was added 2-allylphenol (0.284 g, 2.12
mmol) at room temperature. After stirring the reaction
mixture for 4 h the solvent was evaporated to dryness
to leave a pasty material. Addition of hexane (7 ml) and
ensuing storage of the resulting solution at −70°C for
overnight caused separation of a colorless solid, white
was collected by filtration, and washed with hexane (2
ml ×2), ether (3 ml ×2) at 0°C to afford 7 (118 mg,
28%). IR (KBr): 1600 cm−1 (w(CꢀC)). 1H-NMR
(CDCl3, 500 MHz, l): 1.05 (d, 3H, J=3 Hz, J(PtH)=
68 Hz, Pt–CH3), 1.53 (bd, 9H, J=11 Hz, J(PtH)=39
J=3 Hz, P(CH3)3), 3.38 (d, 2H, J=5 Hz,
CH2CHꢀCH2), 4.97 (dd, 1H, J=10.2 Hz,
CH2CHꢀCH2), 5.05 (dd, 1H, J=17,
–
–
Hz,
2
–CH2CHꢀCH2), 5.30 (q, 1H, J=7 Hz, CH(CF3)2),
5.80 (bs, 1H, –OH), 6.05 (m, 1H, –CH2CHꢀCH2), 6.45
(m, 1H, aromatic), 6.97 (m, 2H, aromatic), 7.12 (m, 1H,
aromatic), 7.40 (m, 4H, aromatic), 7.56 (m, 1H, aro-
matic). 13C{1H}-NMR (125 MHz, CDCl3, l): −12.1
(t, J=7 Hz, Pd–CH3), 12.9 (t, P(CH3)3), 35.0 (–
CH2CHꢀCH2), 72.3 (q, J=7 Hz), 114.3 (–
CH2CHꢀCH2), 138.8 (–CH2CHꢀCH2), 112.9, 118.7,
123.8, 126.1, 126.7, 127.8, 128.3, 128.9, 136.2, 167.9
(aromatic). 31P{1H}-NMR (200 MHz, CDCl3, l): −
13.6 (s). Anal. Calcd for C24H37F3O2P2Pd: C, 49.45; H,
6.40. Found: C, 49.46; H, 6.68.
3.4. Preparation of PtMe(OC6H4CH2CH
ꢀCH2-o)(dppp), (5)
To
an
Et2O
(4
ml)
solution
of
Pt-
Me(OCH(CF3)2)(dppp) (273 mg, 0.35 mmol) was added
2-allylphenol (59 mg, 0.7 mmol) at room temperature.
Stirring the reaction mixture for 4 h caused separation
of a white solid which was collected by filtration,
washed with hexane, and dried in vacuo to give 5 (156
1
mg, 60%). IR (KBr): 1636 cm−1 (w(CꢀC)). H-NMR
(CDCl3, 500 MHz, l): 0.43 (dd, 3H, J=3.16 Hz

Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
47
Table 3
Hz, P(CH3)3), 3.18 (d, 1H, J=18 Hz, –CH2CHꢀCH2),
Crystallographic Data for 4 and 7
3.31 (d, 1H, J=15 Hz, –CH2CHꢀCH2), 4.00 (bd,
2H,–CH2CHꢀCH2), 5.05 (m, 1H, –CH2CHꢀCH2),
6.54 (m, 1H, aromatic), 6.83 (m, 1H, aromatic), 6.91
(m, 1H, aromatic), 7.12 (m, aromatic). 13C{1H}-NMR
(125 MHz, CDCl3, l): 11.0 (d, J=9 Hz, Pt–CH3),
13.9 (d, J=43 Hz, J(PtC)=43 Hz, P(CH3)3), 35.2 (s,
J(PtC)=23 Hz, –CH2CHꢀCH2), 79.2 (s, J(PtC)=46
Compound
4
7
Formula
C24H37O2P2F3Pd
582.90
C
13H21OPPt
Formula weight
Crystal size (mm)
Crystal system
Space group
419.37
0.2×0.7×0.7
Monoclinic
P21/n (no.14)
11.602(6)
17.290(7)
7.424(4)
108.55(3)
1411
0.4×0.5×0.5
Monoclinic
P21/n (no. 14)
10.813(7)
16.872(10)
15.661 (7)
97.71(4)
2831
Hz, –CH2CHꢀCH2), 97.8 (s, J(PtC)=46 Hz,
–
˚
a (A)
˚
CH2CHꢀCH2), 115.2, 120.3, 121.8, 128.9, 130.3, 162.6
(aromatic). 31P{1H}-NMR (200 MHz, CDCl3, l): 29.6
(s, J(PtP)=3826 Hz). Anal. Calcd for C13H21OPPt: C,
37.23; H, 5.06. Found: C, 37.25; H, 5.09.
b (A)
˚
c (A)
i (°)
3
˚
V (A )
Dcalcd (g cm−3
)
1.367
1.973
4
101.32
800
130
55.0
3358
1522
0.098
Cooling the filtrate obtained by separation of 7 at
−70°C caused separation of complex 6 as a colorless
solid (80 mg, 16%).
Z
4
7.93
1200
293
55.0
6718
4393
0.045
v (cm−1
F(000)
)
No. of variables
2qmax (°)
3.6. Preparation of cis-PtMe(OC6H4CH2CH
ꢀCH2-o)(PEt3)2, (8)
Unique reflections
Used reflections (I]3|(I))
R(Fo)a
Rw (Fo)a
0.042
0.086
To an ether solution (5 ml) containing cis-
PtMe2(PEt3)2 (0.486 g, 1.05 mmol) was added
1,1,1,3,3,3-hexafluoro-2-propanol (83 mg, 0.49 mmol)
at room temperature. After stirring the reaction mix-
ture for 6 h the solvent was evaporated to dryness to
leave a colorless oily material. It was dissolved in an
ether (5 ml) solution of 2-allylphenol (66 mg, 0.498
mmol). Stirring the solution was continued for 12 h at
room temperature, and then the solvent was fully
evaporated to give an oily material. Addition of hex-
ane (5 ml) to the product and ensuing storage of the
resulting solution at −20°C overnight caused separa-
tion of a white solid which was collected by filtration
and washed with hexane (3 ml ×2) to give 8 (0.138 g,
48%). IR (KBr): 1634 cm−1 (w(CꢀC)). 1H-NMR
(CDCl3, 500 MHz, l): 0.51 (dd, 3H, J=3.7 Hz
J(PtH)=49 Hz, Pt–CH3), 1.16 (m, 9H, P(CH2CH3)3),
1.80 (m, 6H, P(CH2CH3)3), 3.48 (d, 2H, J=7 Hz,
a R=SꢀFoꢁ−ꢁFcꢀ)/SꢁFoꢁ, Rw=[Sw(ꢁFoꢁ−ꢁFcꢁ)2/Sw(Fo)2]1/2 where
w=[{|(Fo)}2]−1
.
phy were obtained by recrystallization from Et2O-hex-
ane and THF-hexane mixtures, respectively, and
mounted in glass capillary tubes under argon. The unit
cell parameters were obtained by least-squares refine-
ment of setting angles of 20 reflections with 2052q5
30°. Intensities were collected on a Rigaku AFC-SR
automated four-cycle diffractometer by using Mo-Kh
˚
radiation (u=0.71069 A) and the ꢀ-2q method. Cal-
culations were carried out by using a program package
TEXSAN on a DEC Micro VAXII computer. A full
matrix least-squares refinement was carried out by ap-
plying anisotropic thermal factors to all the non-hy-
drogen atoms. Hydrogen atoms were located from
calculation by assuming the ideal positions (d(C–H)=
–CH2CHꢀCH2), 5.01 (dd, 1H, J=9.1 Hz,
CH2CHꢀCH2), 5.10 (dd, 1H, J=17.2 Hz,
–
–
˚
0.95 A) and included the structure calculation without
CH2CHꢀCH2), 6.12 (m, 1H, –CH2CHꢀCH2), 6.50 (m,
aromatic), 7.00 (m, aromatic). 13C{1H}-NMR (125
MHz, CDCl3 l): 5.02 (dd, J=8.92 Hz, Pt–CH3), 8.39
(d, P(CH2CH3)3), 15.1 (d, J=24 Hz, P(CH2CH3)3),
16.7 (d, J=3, J(PtC)=40 Hz, P(CH2CH3)3), 34.9 (s,
–CH2CHꢀCH2), 113.9 (–CH2CHꢀCH2), 139.6 (–
CH2CHꢀCH2), 112.7, 119.5, 126.1, 128.1, 130.1, 165.8.
31P{1H}-NMR (200 MHz, CDCl3, l): 2.79, 22.3 (d,
J=10 Hz, J(PtP)=3869, 1722 Hz). Anal. Calcd for
C22H42OP2Pt: C, 45.59; H, 7.30. Found: C, 45.56; H,
7.41.
further refinement of the parameters. Absorption cor-
rection by „ scan method of the collected data was
applied. Crystallographic data and atomic coordinates
of the non-hydrogen atoms are listed in Tables 3–5.
Hydrogen atoms of 4 were located by calculation as-
˚
suming the ideal geometry (d(CH)=0.95 A) and fixed
throughout the structural calculation except for the
OH hydrogen which was located in final D-map and
refined isotropically. Hydrogen atoms of 7 were lo-
cated by calculation. C1, C2 and C13 were refined
isotropically, whereas the other non-hydrogen atoms
were refined anisotropically. Insufficient convergence
of the structural calculation of 7 is due to the an-
isotropic shape of the crystal with a large absorption
3.7. X-ray structure determination
Crystals of 4 and 7 suitable for X-ray crystallogra-

48
Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
Table 4
Acknowledgements
Atomic coordinates and isotropic temperature factors for 4
This work was supported by the agreement program
of Japan Society for the Promotion of Science (JSPS)
and the Korea Science and Engineering Foundation
(1995) and partly by the Basic Science Research Insti-
tute Program (No. BSRI-96-3440), Korean Ministry of
Education. We are grateful to Dr. Masako Tanaka and
Mr. Jun-Chul Choi of Tokyo Institute of Technology in
Japan for X-ray analyses.
Atom
x
y
z
Beq
Pd
P(1)
P(2)
F(1)
F(2)
F(3)
0(1)
0(2)
0.77570(4)
0.7640(1)
0.7724(1)
0.9914(4)
0.9881(4)
0.8279(4)
0.9724(3)
0.9771(4)
0.5835(4)
1.0502(4)
1.1807(5)
1.2584(5)
1.2160(6)
1.0896(6)
1.0078(5)
1.2337(5)
1.2597(8)
1.2671(8)
0.7310(8)
0.9040(6)
0.6501(7)
0.7335(6)
0.9187(6)
0.6647(7)
0.8753(5)
0.9219(7)
0.7901(6)
0.8378(6)
0.7573(10)
0.6323(10)
0.5847(7)
0.6640(6)
0.979(4)
0.35260(3)
0.3991(1)
0.31118(10)
0.1161(3)
0.0418(3)
0.0529(3)
0.3371(2)
0.2038(3)
0.3622(4)
0.3942(3)
0.3854(3)
0.4467(4)
0.5177(4)
0.5271(3)
0.4675(3)
0.3101(4)
0.2467(5)
0.2507(6)
0.5033(4)
0.3897(5)
0.3561(6)
0.3869(4)
0.2737(4)
0.2319(4)
0.1625(3)
0.0941(5)
0.1343(3)
0.1082(4)
0.0786(1)
0.0779(5)
0.1046(5)
0.1328(4)
0.259(4)
0.79734(3)
0.93451(10)
0.65706(9)
0.7662(3)
0.8751(3)
0.7814(2)
0.8249(2)
0.9129(3)
0.7755(4)
0.8116(3)
0.8340(3)
0.8185(4)
0.7815(4)
0.7612(4)
0.7761(3)
0.8741(4)
0.8151(6)
0.7369(6)
0.9385(5)
1.0074(4)
0.9945(4)
0.5753(4)
0.6322(4)
0.6235(4)
0.8728(4)
0.8243(5)
0.9342(4)
1.0149(4)
1.0694(5)
1.0443(6)
0.9656(6)
0.9108(4)
0.884(3)
3.719(9)
4.88(4)
4.78(4)
11.1(2)
9.8(1)
9.1(1)
4.38(10)
7.0(1)
6.3(2)
3.7(1)
4.2(1)
5.3(2)
5.6(2)
5.2(2)
4.2(1)
5.5(2)
8.7(3)
10.0(3)
10.8(3)
9.9(3)
10.6(3)
7.5(2)
7.4(2)
8.3(2)
5.0(2)
7.0(2)
4.8(2)
6.6(2)
8.7(3)
8.9(3)
8.4(3)
6.5(2)
11.0(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
H(1)
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(1983) 395. (b) M. Brookhart, M.L.H. Green, L.-L. Wong,
Prog. Inorg. Chem. 36 (1988) 1. (c) R.H. Crabtree, Chem. Reu
85 (1985) 245. (d) C. Hall, R.N. Perutz, Chem. Rev. 96 (1996)
3125.
coefficient. Atomic coordinates of hydrogen atoms and
all bond distances and angles are available from the
author (Y.J.K.).
Table 5
Atomic coordinates and isotropic temperature factors for 7
Atom
x
y
z
Beq
Pt
P
O
0.0323(1)
0.21920(9)
0.1663(7)
0.256(2)
0.334(3)
0.325(2)
0.352(2)
0.376(2)
0.325(2)
0.345(2)
0.416(3)
0.469(3)
0.450(3)
0.118(2)
0.141(3)
0.082(3)
0.226(3)
0.3667(2)
0.081(1)
0.641(3)
0.265(5)
0.307(4)
0.485(4)
0.653(4)
0.713(4)
0.870(4)
0.952(5)
0.885(5)
0.730(5)
0.460(4)
3.52(3)
4.4(2)
4.9(7)
5.4(8)
4.8(9)
4.6(9)
3.7(9)
3.6(9)
3.7(8)
4.0(1)
5.0(1)
5.0(1)
4.0(7)
6.0(1)
6.0(1)
8.0(1)
−0.0380(8)
0.114(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
0.030(3)
−0.072(3)
−0.093(2)
0.018(3)
0.111(3)
0.213(3)
0.219(3)
0.126(4)
0.023(3)
0.081(3)
0.084(3)
[13] (a) D.P. Arnold, M.A. Benett, M.S. Bilton, G.B. Robertson, J.
Chem. Soc. Chem. Commun. (1982) 115. (b) H.E. Bryndza,
J.C. Calabrese, M. Marsi, D.C. Roe, W. Tam., J.E. Bercaw, J.
Am. Chem. Soc. 108 (1986) 4805.
−0.013(5)
0.059(5)
−0.107(6)
−0.125(3)
−0.151(4)

Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41–49
49
[16] R.A. Love, T.F. Koetzle, G.J.B. Williams, L.C. Andrews, R. Bau,
Inorg. Chem. 14 (1975) 2653 and related references therein.
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Jpn. 54 (1981) 1868.
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Organometallics 8 (1989) 2907.
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(1976) 993. (b) T.G. Appleton, M.A. Bennett, Inorg. Chem. 17
(1978) 738. (c) M.A. Bennett, T. Yoshida, J. Am. Chem. Soc. 100
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Chem. 175 (1979), 239. (e) D.P. Arnold, M.A. Bennett, J.
Organomet. Chem. 199 (1980) 119.
[15] R.H. Crabtree, The Organometallic Chemistry of the Transition
Metal (2nd edn.), New York, 1994, p. 107.
.