Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)-rhodium(III) Bearing Bis(diphenylphosphanylmethyl)phenylphosphane

Article abstract of DOI:10.1002/ejic.200300402

Reaction of [Cp*RhCl₂]₂ (1) with bis(diphenylphosphanylmethyl)phenylphosphane (dpmp) in the presence of KPF ₆ generated the mono- or bi-nuclear complexes [(Cp* RhCl)(dpmp-P,P,P)(RhCl₂Cp*)](PF₆) (2) or [Cp*RhCl(dpmp-P,P)](PF₆) (3), depending on the reaction conditions. These complexes have two chiral centers at Rh and the central P atoms, and the diastereomers were separated by successive recrystallization. The structures of 2(B) with an R_RhSp/S_RhR_P pair and 3(A) with an R_RhSp/S_RhR_p pair were elucidated by X-ray analyses. Reaction of 1 with an excess of dpmp in the presence of Ag(OTf) generated a hetero-tetranuclear complex [{Cp*RhCl ₂(dpmp-P,P,P)Ag}₂](OTf)₂ (4). An X-ray analysis revealed that each Cp*RhCl₂ moiety is connected by a terminal P¹ atom of the dpmp ligand and each Ag atom is two-coordinate and is surrounded by another terminal P³ atom, and a central P*³ atom of the other dpmp ligand. A mixture of 1 and dpmp was treated with Au(SC₄H₈) or CuCl in the presence of KPF₆, generating the hetero-tetranuclear complexes [{Cp*RhCl₂(dpmp-P,P,P)M}₂](PF₆) ₂ (7: M = Au; 8: M = Cu), in which the structures, except for the Cl-bridged structure of 8, are fundamentally similar to that of 4. These complexes were also prepared by the reactions of 3 with Au(SC₄H ₈) or CuCl. Complex 3 reacted with AgOTf to afford [Cp*Rh(dpmp-P,P,P)](OTf)₂ (5). Treatment of 3(A) (a diastereomer with an R_RhS_P2/S_RhR_P2 pair) with 1, [(p-cymene)RuCl₂]₂ or PdCl₂(cod) gave [Cp*RhCl(dpmp-P,P,P)RhCl₂Cp*](PF₆) (2) or [Cp*RhCl(dpmp-P,P,P)RuCl₂(p-cymene)](PF₆) (6), respectively. These addition reactions proceeded stereoselectively. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300402

FULL PAPER
Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)-
rhodium(III) Bearing Bis(diphenylphosphanylmethyl)phenylphosphane
Yasuhiro Yamamoto,*[a] Yosuke Kosaka,[a] Yoshihiro Tsutsumi,[a] Yoshihiro Kaburagi,[a]
Katsuaki Kuge,[b] Yusuke Sunada,[b] and Kazuyuki Tatsumi[b]
Keywords: Rhodium / Gold / Copper / Silver / Cluster compounds / P ligands
Reaction of [Cp*RhCl2]2 (1) with bis(diphenylphosphanyl-
methyl)phenylphosphane (dpmp) in the presence of KPF6
generated the mono- or bi-nuclear complexes [(Cp*
atom, and a central P*2 atom of the other dpmp ligand. A
mixture of 1 and dpmp was treated with Au(SC4H8) or CuCl
in the presence of KPF6, generating the hetero-tetranuclear
RhCl)(dpmp-P,P,P)(RhCl2Cp*)](PF6) (2) or [Cp*RhCl(dpmp- complexes [{Cp*RhCl2(dpmp-P,P,P)M}2](PF6)2 (7: M = Au; 8:
P,P)](PF6) (3), depending on the reaction conditions. These
complexes have two chiral centers at Rh and the central P
atoms, and the diastereomers were separated by successive
M = Cu), in which the structures, except for the Cl-bridged
structure of 8, are fundamentally similar to that of 4. These
complexes were also prepared by the reactions of 3 with
recrystallization. The structures of 2(B) with an RRhSP/SRhRP Au(SC4H8) or CuCl. Complex 3 reacted with AgOTf to afford
pair and 3(A) with an RRhSP/SRhRP pair were elucidated by
X-ray analyses. Reaction of 1 with an excess of dpmp in the
presence of Ag(OTf) generated a hetero-tetranuclear com-
[Cp*Rh(dpmp-P,P,P)](OTf)2 (5). Treatment of 3(A) (a diastere-
omer with an RRhSP2/SRhRP2 pair) with 1, [(p-cymene)RuCl2]2
or PdCl2(cod) gave [Cp*RhCl(dpmp-P,P,P)RhCl2Cp*](PF6) (2)
plex [{Cp*RhCl2(dpmp-P,P,P)Ag}2](OTf)2 (4). An X-ray ana- or [Cp*RhCl(dpmp-P,P,P)RuCl2(p-cymene)](PF6) (6), respect-
lysis revealed that each Cp*RhCl2 moiety is connected by a
ively. These addition reactions proceeded stereoselectively.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
terminal P1 atom of the dpmp ligand and each Ag atom is
two-coordinate and is surrounded by another terminal P3 Germany, 2004)
Introduction
Recently, we reported the preparation of supramolecular
complexes based on quasi-octahedral geometries of rho-
dium() and iridium() bearing a pentamethylcyclopen-
tadienyl or arene ruthenium() moiety. Thus, the reactions
of [Cp*MCl2(µ-1,4-(CN)2-2,3,5,6-Me4C6)MCl2Cp*] (M ϭ
Rh, Ir; Cp* ϭ C5Me5) with bidentate ligands such as pyra-
zine, bipyridine and di-isocyanide in the presence of AgOTf
(OTf ϭ CF3SO3) generated tetranuclear complexes with a
square core.[3Ϫ5] Recently, self-assembled supramolecules
with the pentamethylcyclopentadienyl or cyclopentadienyl
groups in which the CN group has been generally used as a
binary ligand have been reported by several researchers.[6Ϫ9]
We are interested in the chemistry of the interaction be-
tween quasi-octahedral complexes and dpmp containing
three potential coordination sites because of expectation of
various coordination modes and polynuclear complexes. We
adopted binuclear complexes of rhodium(), iridium() or
ruthenium() containing pentamethylcyclopentadienyl or
arene groups as quasi-octahedral complexes, for which the
chemistry has not yet been developed. Here we report the
preparation and stereochemistry of mononuclear, binuclear
and polynuclear complexes of rhodium() bearing dpmp
and pentamethylcyclopentadienyl ligands. Part of this work
has already been briefly reported.[10]
Triphosphanes, especially bis(diphenylphosphanylmethyl)-
phenylphosphane (dpmp), play an important role as the
backbone in the construction of polynuclear clusters. The
chemistry of rhodium, iridium, and gold has been sited by
Balch.[1] We have developed systematic syntheses of homo-
and hetero-bimetallic and -trimetallic platinum and pal-
ladium clusters with tridentate phosphane and isocyanide
ligands.[2] These complexes are constructed fundamentally
of a square planar framework and contain dpmp, carbon
monoxide, halogens and isocyanides as ligands. Octahedral
complexes can lead to compounds with diverse dimen-
sionality, in comparison with square-planar complexes.
[‡]
Present adress: The Institute of Scientific and Industrial
Research, Osaka University, Mihogaoka, Ibaraki, Osaka 567-
0047, Japan. E-mail: yamamo24@sanken.osaka-u.ac
[a]
Department of Chemistry, Faculty of Science, Toho University,
Miyama 2-2-1, Funabashi, Chiba 274-8510, Japan
[b]
Research Center for Materials Science and Department of
Chemistry, Graduate School of Science, Nagoya University,
Furo-cho, Chikusa-ku, Nagoya 454-8602, Japan
E-mail: i45100a@nucc.cc.nagoya-u.ac.jp
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
134
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DOI: 10.1002/ejic.200300402
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Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)rhodium(III)
FULL PAPER
Results and Discussion
of 2:1, which were separated by successive recrystallization.
The X-ray study of 3(A) revealed its stereochemistry to be
that of the diastereomer with an RRhSP/SRhRP pair (anti-
form), based on the priority order of the ligands.[10] Thus
3(B) is assumed to be the RRhRP/SRhSP pair (syn-form).
The geometries around the Rh and P2 centers were found
to be similar for 2(A) and 3(A), and for 2(B) and 3(B). In
Reactions of [Cp*RhCl2]2 (1) with dpmp in the Presence of
KPF6 or AgOTf
When [Cp*RhCl2]2 (1) (Cp* ϭ C5Me5) was treated with
an equivalent of dpmp in the presence of KPF6 at room
temperature, two kinds of complexes [2(A) and 2(B)] with
the empirical formula of [Cp*2Rh2Cl3(dpmp-P, P, P )](PF6)
were isolated by successive recrystallization (Scheme 1). The
IR spectrum of 2 showed a peak at ca. 845 cmϪ1 consistent
1
the H NMR spectra, the Cp* protons appeared at δ ϭ
1.74(t) for 3(A) and at δ ϭ 1.78 for 3(B). In the 31P{1H}
NMR spectrum of 3, the chemical shifts (δ ϭ Ϫ24 ഠ Ϫ30)
of the free P nuclei appeared at the higher magnetic fields
by ca. 10 ഠ 20 ppm than those found for the coordinated
P nuclei.[11]
1
with the presence of a PF6 anion. The H NMR spectrum
of the reaction mixture indicated a ratio of 1.1:1.0 for
2(A):2(B). The Cp* protons appeared at δ ϭ 1.28 (d) and
1.55 (t) for 2(A) and at δ ϭ 1.27 (d) and 1.73 (t) for 2(B),
respectively. The chemical shift of the Cp* protons in the
chelate ring moiety appeared at a lower magnetic field than
those of the other Cp* protons since the Rh atom in a che-
late ring is sufficiently electron-deficient for the transfer
electron density from the Cp* ligand to the rhodium center.
The X-ray analysis of 2(B) revealed that a Rh atom is con-
nected by the terminal and the central P atoms, and another
Rh atom is coordinated to another terminal P atom.[10]
The molecule has two chiral centers namely the Rh and
the central P2 atom. Based on the priority order of the li-
gands around the two chiral centers,[10] compound 2(B) was
identified as the diastereomer with an RRhSP/SRhRP pair.
Thus 2(A) is the diastereomer with an RRhRP/SRhSP pair.
The stereochemical difference is that the Cl atom and the
P-substituted Ph group occupy the opposite side in 2(A)
and the same side in 2(B), where the structure of a 2(A)
type is designated as an anti-form and that of a 2(B) type
as a syn-form.
Complex 3(A) or 3(B) was treated with 1 at room tem-
perature, exclusively generating 2(A) or 2(B), respectively.
The reactions proceeded stereospecifically. Complex 2(A)
was treated with dpmp at room temperature, affording a
mixture of 3(A) and 3(B) consisting of an approximately 5:1
molar ratio. A similar reaction of 2(B) gave a mixture of
3(A) and 3(B) consisting of an approximately 1:2 molar ra-
tio (Scheme 2). The ratios are reasonable on the basis of the
formation ratio in the original reaction of 1 with dpmp. In
these reactions the conversion from 2(B) to 3 and its reverse
reaction are slower than inter-conversion between 2(A)
and 3.
Isomerization from 2(A) [or, 3(A)] to 2(B) [or, 3(B)] and
its reverse reaction did not occur on standing for a long
period of time (Ͼ100 h) at room temperature. When com-
pound 2(A) was treated with xylyl isocyanide in acetone at
reflux, cleavage of the RhϪP3 bond occurred, generating
3(A) and Cp*RhCl2(XylNC) (Scheme 2). This reaction sug-
gests a greater bond strength in the chelate ring.
The reaction of 1 with an excess of dpmp in the presence
A similar reaction of 1 with dpmp was carried out in the
of KPF6 afforded yellow crystals of [Cp*RhCl(dpmp)](PF6) presence of two equivalents of Ag(OTf) which afforded an
(3). The 1H NMR spectrum of the reaction mixture consists orange-yellow complex 4, formulated as [{Cp*RhCl2-
of two sets of isomers, 3(A) and 3(B), with an intensity ratio (dpmp-P, P, P )Ag}2] (OTf)2 (Scheme 1). The structure was
Scheme 1. Reactions of [Cp*RhCl2]2 1 with dpmp in the presence of KPF6 or Ag(OTf)
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135

Y. Yamamoto et al.
FULL PAPER
Scheme 2. Reactions of 2 with dpmp or xylyl isocyanide, where the PF6 anion has been omitted for clarity. The formation ratio of 3(A)
and 3(B) is designated in the bracket [].
subsequently confirmed by X-ray analysis (Figure 1). Each Reactions of [Cp*RhCl(dpmp-P,P)](PF6) and [Cp*2Rh2Cl3-
Cp*RhCl2 moiety is connected by a terminal P1 atom of (dpmp-P,P,P)](PF6)
the dpmp ligand. Each Ag atom is two-coordinate and is
The mononuclear complex 3 was anticipated as being a
surrounded by another terminal P3 atom and a central P*2
potential precursor to hetero- or homo-multiple nuclear
atom of the other dpmp ligand. It is interesting to note that
complexes. The reactions of 3 are depicted in Scheme 3.
4 was isolated as an addition product without the abstrac-
In order to try to extract a Cl anion, 3 was treated with
tion of Cl anions by Ag(OTf).
an excess of KPF6, but only the starting material could be
recovered. A similar reaction with AgOTf, however, gave
the yellow η3-complex [Cp*Rh(dpmp-P, P, P )](OTf)2 (5)
bearing a tridentate ligand as evidenced by the presence of
a quadruplet for the Cp* protons in the 1H NMR spectrum.
The X-ray analysis was in agreement with the proposed
structure (Figure 2).
When 3(A) was treated with [(p-cymene)RuCl2]2 at room
temperature, a reaction readily occurred, generating a
brown complex 6(A) established from elemental analysis
and FAB mass spectrometry as [Cp*RhCl(dpmp-
P, P, P )RuCl2(p-cymene)](PF6). In the 1H NMR spectrum,
the Cp* protons appeared at δ 1.52 as a triplet and the
methyl protons of the isopropyl group showed two doublets
at δ ϭ 0.52 and 1.00, due to nonequivalence arising from
the chiral centers. The 31P{1H} NMR spectrum showed
1
2
three resonances at δ ϭ Ϫ12.0 (dt, JRhP2 ϭ JP2P1 ϭ 97.0,
2JP2P3 ϭ 55.5 Hz, P2), Ϫ1.41 (t, 1JP1Rh ϭ 2JP1P2 ϭ 97.0 Hz,
P1) and 23.7 (d, JP3P2 ϭ 55.5 Hz, P3) for the dpmp ligand.
2
Figure 1. Molecular structure of 4.H2O; the OTf anion and H2O The stereochemistry with the anti-form (RRhRP2/SRhSP2) of
have been omitted for clarity and thermal ellipsoids have been
the starting complex is assumed to be retained. Complex 6
was also prepared from the reaction of 1 with [(p-cy-
drawn at the 50% probability level.
mene)RuCl2]2 in a 1:1 molar ratio in the presence of KPF6.
Crystallization of the reaction mixture gave two dia-
In the H NMR spectrum, the Cp* protons appeared at stereomers in a 52% yield, consisting of a 1:2 molar ratio
1
δ ϭ 1.25 as a doublet, suggesting a symmetric structure. of 6(A) and 6(B), suggesting that a chelating formation in-
The 31P{1H} NMR spectrum showed a double doublet at cluding a Rh atom is preferable to one with a Ru atom. In
1
δ ϭ 28.6 (JPRh ϭ 146, JP,P ϭ 12.9 Hz) due to the P1 nucleus the H NMR spectrum of 6(B), the Cp* protons appeared
coordinated to the rhodium atom and the unresolved sig- at δ ϭ 1.73 and two doublets for the isopropyl protons re-
nals around δ ϭ 2.6 are due to the other P nuclei.
sulted in magnetic non-equivalence. The 31P{1H} NMR
136
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Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)rhodium(III)
FULL PAPER
Scheme 3. Reactions of 3(A), where the PF6 anions have been omitted for clarity.
of 1:2 due to the Cp* protons, suggesting the presence of
diastereomers arising from two chiral centers (the central P
atom of dpmp). Crystals of 8(A) were suitable for X-ray
analysis. The structure, except for the presence of two Cl
bridges, is essentially similar to those of 4 and 7. The stereo-
chemistry was confirmed as an RP2SP2*/SP2RP2* pair (Fig-
ure 3). Thus complex 8(B), with the chemical shift of δ ϭ
1.08, is assumed to be a diastereomer with an RP2RP2*
/
SP2SP2* pair.
Figure 2. Molecular structure of the cation of 5; the OTf anions
have been omitted for clarity and thermal ellipsoids have been
drawn at the 50% probability level.
spectrum showed three resonances at δ ϭ Ϫ13.8 (dt,
2
1JRhP2
1JP1Rh
ϭ
ϭ
2JP2P1 ϭ 105, JP2P3 ϭ 55.0 Hz, P2), Ϫ10.2 (t,
2JP1P2 ϭ 109.0 Hz, P1) and 26.6 (d, JP3P2
ϭ
2
55.0 Hz, P3) for the dpmp ligand.
Complex 3(A) reacted readily with AuCl(SC4H8) at room
temperature, giving the reddish brown complex 7 [{Cp*
RhCl2(dpmp-P, P, P )Au}2](OTf)2. X-ray analysis confirmed
Figure 3. Molecular structure of 8·2CH2Cl2; the OTf anions and
CH2Cl2 molecules have been omitted for clarity and thermal ellip-
that the molecular structure is fundamentally similar to that soids have been drawn at the 50% probability level.
of 4.[10] Complex 7 was directly generated from 1,
AuCl(SC4H8) and dpmp in the presence of KPF6.
A one-pot synthesis from 1, an excess of dpmp and CuCl
Copper() chloride reacted with 3(A) at room tempera- in the presence of KPF6 can also be used to prepare a mix-
ture, generating the orange complex [{Cp*RhCl2(dpmp- ture of the diastereomers of 8. The BF4 anion complex was
1
P, P, P )Cu}2](PF6)2 (8). The H NMR spectrum showed two obtained from the reaction of 1 with dpmp in the presence
doublets at δ ϭ 1.08 and 1.20 ppm with an intensity ratio of [Cu(MeCN)4](BF4).
Eur. J. Inorg. Chem. 2004, 134Ϫ142
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Y. Yamamoto et al.
FULL PAPER
Complex 3(A) was treated with S8 at room temperature, mely the two Rh centers and a P2 atom, formation of two
affording an orange compound formulated from elemental diastereomers was expected. However, no isomers were de-
1
analysis and FAB mass spectrometry as [Cp*RhCl(dpmp- tected in the H NMR spectrum. The stereochemistry for
P, P, P )S](PF6) 9 (Scheme 4). The molecular structure is as- the chelating group in 10 was maintained, but the geometry
sumed to be consistent with addition of a S atom to the around the other Rh center remains unknown.
free terminal P3 atom. This reaction is similar to the usual
reaction of tertiary phosphanes with sulfur.
Possible Pathway
A possible route to a hetero-nuclear complex from 1 con-
sists of the initial formation of [Cp*RhCl(dpmp-P, P )]Cl A,
followed by substitution of a Cl anion with the PF6 or OTf
anions to form B and AgCl (or KPF6) (Scheme 6). This
proposal was confirmed by the fact that in separate experi-
ments, complex A was prepared by the reaction of 1 with
an excess of dpmp, and subsequently treated with KPF6,
generating 3. The next process is the coordination of the
resultant AgCl to the free P atom of 3, generating an inter-
mediate C.
This type of species has been isolated as [Cp*IrCl(dpmp-
P, P, P )AuCl](PF6)[12] or [(C6Me6)Ru(dpmp-P, P, P )AuCl]-
(PF6)[10] by the reactions of [Cp*IrCl(dpmp-P, P )](PF6) or
[(C6Me6)Ru(dpmp-P, P, ](PF6) with AuCl(SC4H8). Finally,
dimerization of D resulting in a nucleophilic attack of the
Cl anion to the Rh atom led to formation of tetranuclear
complexes.
Scheme 4. Reactions of 3(A) with sulfur
The substitution reaction of 2(A) with xylyl isocyanide
(XylNC) in the presence of KPF6 was unsuccessful, leading
only to recovery of the starting materials. The reaction in
the presence of Ag(OTf), however, gave [(Cp*RhCl)2-
(dpmp-P, P, P )(XylNC)](OTf)2 (10) (Scheme 5). The pres-
ence of a terminal isocyanide ligand was confirmed by ap-
pearance of a ν(NϵC) band at 2168 cmϪ1 and disappear-
ance of a PF6 band at ca. 850 cmϪ1. The H NMR spec-
1
trum exhibited two resonances at δ ϭ 1.48(t) and 2.00(d)
for the Cp* protons. The 31P{1H} NMR spectrum showed
three resonances at δ ϭ Ϫ15.5(ddd), Ϫ2.76(dd) and
Molecular Structures
Crystal Structure of 5: A perspective drawing of 5 with
28.6(dd) due to the P2, P1 and P3 nuclei, respectively. These the atomic numbering scheme is given in Figure 2, and
spectroscopic data suggest the structure depicted in selected bond lengths and angles are listed in Table 1. The
Scheme 5. Since this complex has three chiral centers na- dpmp ligand acts as a tridentate ligand. The average
Scheme 5. Reactions of 2(A) with xylyl isocyanide in the presence of AgOTf
Scheme 6. Possible pathway for the formation of the hetero-tetranuclear complexes, where MX ϭ AgOTf, [Cu(MeCN)4](PF6) or
AuCl(SC4H8) and MCl ϭ AgCl, CuCl or AuCl.
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Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)rhodium(III)
FULL PAPER
PϪRhϪP bite angle has a typical value of 70.9°, except for ters.[10] However, the measured Ag···Ag separation of 3.385
˚
the P(1)ϪRhϪP(3) bite angle of 95.2°. The latter wide an- A in 4 suggests the absence of a metalϪmetal bond, since
gle is a result of an unrestrained angle by a methylene chain. the AgIϪAgI separations of 3.162Ϫ3.223
A
in
˚
˚
The Rh(1)ϪP(3) length of 2.369(4) A is longer by ca. 0.05 [Ag3{HC(PPh2)3}] have also suggested the absence of me-
A than the average value of other RhϪP bonds.
tal-metal bonds.[14] In comparison, [Ag2(dpmp)2](NO3)2,
˚
Structures of 4·H2O and 8·2CH2Cl2: Perspective drawings which is considered to have an AgϪAg bond has an
[15]
˚
of 4 and 8 with the atomic numbering scheme are given in AgϪAg separation of 3.085(1) A.
A Cu···Cu separation
˚
Figure 1 and Figure 3, and selected bond lengths and angles of 3.566 A in 8 is indicative of the absence of a metal-me-
are listed in Table 2 and Table 3. Complexes 4 and 8 contain tal bond.
˚
one H2O and two CH2Cl2 solvate molecules, respectively.
Since the M···Cl separations of 2.709 and 2.911 A in 4
˚
Complexes 4 and 8 both have a crystallographically im- [M ϭ Ag], and of 3.05 and 3.15 A in 7 [M ϭ Au] are longer
posed inversion center in the middle of the Ag···Ag* and than those found in each of the MϪCl-bridged bonds,[16]
Cu···Cu vectors like that in the Au···Au vector in 7.[10] The the Ag atoms are two-coordinate and are surrounded by
eight M2P4C2 rings (M ϭ Ag, Au, Cu) adopt a chair form two P atoms (a terminal P3* atom from a dpmp ligand and
to relieve the steric repulsion of the phenyl groups. Each a central P2 atom from another dpmp). The P(2)ϪMϪP(3)*
Cp*RhCl2 moiety is connected by a terminal P1 atom of angles are 150.3(1)° for 4 and 164.6(1)° for 7, bent from the
the dpmp ligand. These compounds have two chiral centers linear array to the reverse side against another Ag atom.
(P2 and P2*). The priority order of the ligands is M Ͼ Ph The Cu···Cl(1) separation of 2.443 A can be compared with
˚
Ͼ C2 Ͼ C1 for the central P2 and P2*atoms, where C1 rep- the bridged CuϪCl bond lengths of 2.448(3) A in
˚
resents the methylene carbons between the P1 and P2 atoms [Ir2(H)4Cu(CO)2(µ-Cl)Cl(µ-dpma)2]ϩ
and another
[17]
and C2 is another methylene carbon atom. Complexes 4 Cu···Cl(2) separation of 2.568 A can be assumed to be a
and 8 have been identified as the RP2SP2*/SP2RP2* pairs, weak interaction, although it is somewhat longer. These
˚
similarly to 7.[10]
Cu···Cl interaction cause the P(2)ϪCuϪP(3)* angle
˚
An Au···Au separation of 3.203(2) A in 7 suggests the [145.77(7)°] to be more acute than those found in other
presence of a weak interaction between the two Au cen- complexes.
Table 1. Selected bond lengths and angles for [Cp*Rh(dpmp-P, P, P )](OTf)2 (5)
Rh(1)ϪP(1)
P(1)ϪC(41)
P(3)ϪC(42)
P(1)ϪRh(1)ϪP(2)
Rh(1)ϪP(1)ϪC(41)
P(2)ϪC(42)ϪP(3)
2.324(3)
1.83(1)
1.83(1)
71.0(1)
95.8(4)
95.9(5)
Rh(1)ϪP(2)
P(2)ϪC(41)
2.310(3)
1.81(1)
Rh(1)ϪP(3)
P(2)ϪC(42)
2.369(4)
1.82(1)
P(1)ϪRh(1)ϪP(3)
P(1)ϪC(41)ϪP(2)
C(41)ϪP(2)ϪC(42)
95.2(1)
95.2(5)
104.7(5)
P(2)ϪRh(1)ϪP(3)
Rh(1)ϪP(2)ϪC(42)
70.7(1)
96.7(4)
.
Table 2. Selected bond lengths and angles for [{Cp*RhCl(dpmp-P, P, P )Ag}2](PF6)2 H2O (4·H2O)
Ag(1)ϪCl(2)
Rh(1)ϪCl(1)
P(1)ϪC(13)
2.706(3)
2.425(3)
1.85(1)
Ag(1)ϪP(2)
Rh(1)ϪCl(2)
P(2)ϪC(13)
2.433(3)
2.441(3)
1.85(1)
Ag(1)ϪP(3)*
Rh(1)ϪP(1)
P(2)ϪC(20)
2.392(3)
2.327(3)
1.84(1)
P(3)ϪC(20)
1.84(1)
88.32(9)
89.5(1)
Cl(2)ϪAg(1)ϪP(2)
Cl(1)ϪRh(1)ϪCl(2)
Ag(1)ϪCl(2)ϪRh(1)
Ag(1)ϪP(2)ϪC(13)
Ag(1)ϪP(3)ϪC(20)
Ag(1)···Ag(1)
Cl(2)ϪAg(1)ϪP(3)*
Cl(1)ϪRh(1)ϪP(1)
Rh(1)ϪP(1)ϪC(13)
Ag(1)ϪP(2)ϪC(20)
120.2(1)
P(2)ϪAg(1)ϪP(3)*
Cl(2)ϪRh(1)ϪP(1)
P(1)ϪC(13)ϪP(2)
P(2)ϪC(20)ϪP(3)
150.3(1)
92.7(1)
120.5(6)
112.3(5)
87.7(1)
119.9(4)
112.5(4)
98.8(1)
112.1(4)
116.6(4)
3.385(2)
Table 3. Selected bond lengths and angles for [{Cp*RhCl2(dpmp-P, P, P )Cu}2](PF6)2·2CH2Cl2 (8·2CH2Cl2)
CuϪCl(1)
CuϪP(3)*
RhϪP(1)
P(2)ϪC(30)
Cl(1)ϪCuϪCl(2)
Cl(2)ϪCuϪP(2)
Cl(1)ϪRhϪCl(2)
RhϪCl(2)ϪCu
Cl(2)ϪRh(1)ϪP(1)
3.443(2)
2.235(2)
CuϪCl(2)
RhϪCl(1)
P(1)ϪC(23)
P(3)ϪC(30)
Cl(1)ϪCuϪP(2)
Cl(2)ϪCuϪP(3)*
Cl(1)ϪRhϪP(1)
RhϪP(1)ϪC(23)
2.568(2)
2.421(2)
1.836(7)
1.840(7)
92.02(6)
101.20(6)
89.63(6)
101.0(3)
CuϪP(2)
RhϪCl(2)
P(2)ϪC(23)
2.249(2)
2.440(2)
1.851(7)
2.329(2)
1.839(7)
85.61(6)
95.28(6)
88.99(6)
90.29(6)
88.1(2)
Cl(1)ϪCuϪP(3)*
P(2)ϪCuϪP(3)*
RhϪCl(1)ϪCu
118.80(7)
145.77(7)
93.77(7)
120.0(4)
P(1)ϪC(23)ϪP(2)
Eur. J. Inorg. Chem. 2004, 134Ϫ142
www.eurjic.org
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139

Y. Yamamoto et al.
FULL PAPER
Preparation of [Cp*Rh(dpmp-P,P,P)](OTf)2 (5): A mixture of 3
(50 mg, 0.054 mmol) and AgOTf (75.4 mg, 0.293 mmol) in CH2Cl2
(15 mL) and acetone (5 mL) was stirred at room temperature. After
3 h, the solvent was removed and the residue was extracted with
CH2Cl2. The solution was concentrated and diethyl ether was ad-
ded to form orange crystals (41.8 mg, 72.4%). IR (nujol): ν˜ ϭ 1255,
1153, 1028 cmϪ1 (OTf). UV/Vis (CH2Cl2): λmax ϭ 335, 270 nm. 1H
NMR [(CD3)2CO]: δ ϭ 1.66 (q, JPH ϭ 4.5 Hz, Cp*, 15 H), 5.49
(c, CH2, 4 H), 7.3Ϫ8.4 (c, Ph, 25 H). 31P{1H} NMR [(CD3)2CO]:
The MϪP lengths increase with M in the order Cu, Au
and Ag in accordance with the atomic radii of the metals.
The Cl(1)ϪRhϪCl(2) and ClϪRhϪP(1) angles which are
in the range 87.3Ϫ92.7°are nearly perpendicular as a result
of the octahedral core. The RhϪCl bond lengths in the
˚
range 2.417Ϫ2.440 A are typical.
δ ϭ Ϫ18.2 (dt, JP1P2 ϭ JP1Rh ϭ 97.2 Hz, P1), Ϫ47.4 (q, JP2P1
ϭ
Conclusion
JP2Rh ϭ 97.2 Hz, P2), Ϫ143.6 (sept, JPF ϭ 707.5 Hz, PF6).
C44H44F6O6P3RhS2 (1042.8): calcd. C 50.68, H 4.25; found C
50.99, H 4.38.
The chemistry of dpmp has been limited to square-planar
complexes of palladium, platinum and rhodium as well as
two coordinate complexes of silver and gold. In this paper
the chemistry of dpmp has been extended to the octahedral
geometry. Pentamethylcyclopentadienyl rhodium() com-
plexes bearing a dpmp ligand may be useful in the strategic
synthesis of hetero-polynuclear compounds, where the clus-
ter core could be tuned by the choice of the additional me-
tal complex.
Preparation of [Cp*RhCl(dpmp-P,P,P)RuCl2(p-cymene)](PF6) (6)
(1) From 3(A) and [(p-Cymene)RuCl2]2: A mixture of 3(A) (50.4 mg,
0.054 mmol) and [(p-cymene)RuCl2]2 (19.3 mg, 0.032 mmol) was
stirred in CH2Cl2 (10 mL) at room temperature for 5 h. The solu-
tion was concentrated to ca. 3 mL and diethyl ether was added,
affording the yellow complex 6(A) (43.6 mg, 65.6%). UV/Vis
(CH2Cl2): λmax ϭ 361 nm. IR (nujol): ν˜ ϭ 837 cmϪ1. FAB MS:
m/z ϭ 1085 ([M]ϩ). 1H NMR (CDCl3): δ ϭ 0.53 (d, JH,H ϭ 7.0 Hz,
iPr, 3 H), 1.00 (d, JH,H ϭ 7.0 Hz, iPr, 3 H), 1.52 (t, JH,H ϭ 3.5 Hz,
Cp*, 15 H), 1.75 (s, p-Me, 3 H), 2.41 (sept, JH,H ϭ 7.0 Hz, iPr, 1
H), 4.06 (c, CH2, 2 H), 3.72 (c, CH2, 1 H), 4.92 (c, CH2, 1 H),
5.33, 5.44 (AB system, JH,H ϭ 6.0 Hz, p-cymene), 6.8Ϫ8.4 (m, ph,
Experimental Section
1
2
25 H). 31P{1H} NMR (CDCl3): δ ϭ Ϫ12.0 (dt, JRhP2 ϭ JP2P1
ϭ
All procedures were carried out under a nitrogen atmosphere.
Dichloromethane was distilled from CaH2 and diethyl ether
2
1
2
97.0, JP2P3 ϭ 55.5 Hz, P2), Ϫ1.41 (t, JP1Rh ϭ JP1P2 ϭ 97.0 Hz,
was
distilled
from
LiAlH4.
Isocyanides,[18]
P1) and 23.7 (d, JP3P2 ϭ 55.5 Hz, P3), Ϫ143.5 (sept, JPF
ϭ
2
(Ph2PCH2)2PPh,[19] [Cp*RhCl2]2,[20] and [Cu(MeCN)4](BF4)[21]
were prepared according to the literature. Infrared and electronic
absorption spectra were recorded on FT/IR-5300 and U-best30 in-
struments, respectively. NMR spectra were recorded on a JEOL
JNM-ECL-400 spectrometer. 1H NMR spectra were measured at
400 MHz and 31P{1H} NMR spectra were measured at 161 MHz
using 85% H3PO4 as an external reference.
707.5 Hz, PF6).
(2) Direct Reaction:
A mixture of [Cp*RhCl2]2 (50.0 mg,
0.081 mmol), [(p-cymene)RuCl2]2 (50.9 mg, 0.083 mmol), dpmp
(94.4 mg, 0.186 mmol) and KPF6 (43.1 mg, 0.234 mmol) was
stirred in CH2Cl2 (10 mL) and acetone (10 mL) at room tempera-
ture. After 20 h, the solution was evaporated to dryness and the
residue extracted with CH2Cl2. The CH2Cl2 solution was concen-
trated to ca. 2 mL and diethyl ether was added, affording orange
crystals (45.8 mg, 52.1%). The crystals were mainly isolated as the
diastereomer 6(B) based on the NMR spectrum. The ratio of 6(A)
Supporting Information: See also the footnote on the first page of
this article. (a) Preparation of [(Cp*RhCl)(dpmp-P, P, P )(RhCl2-
Cp*)](PF6) (2). (b) Preparation of [Cp*RhCl(dpmp-P, P )](PF6) (3).
(c) Preparation of [{Cp*RhCl2(dpmp-P, P, P )Au}2](PF6)2 (7). (c) to 6(B) was 1:2.
Crystal structures of 2(B)·CH2Cl2 and 3(A). (d) Table S1. Crystal
6(B): 1H NMR (CDCl3): δ ϭ 0.52 (d, JH,H ϭ 7.0 Hz, iPr, 3 H),
data for [{Cp*2Rh2Cl3(dpmp-P, P, P )}(OTf)2·CH2Cl2 2(B)·CH2Cl2,
[Cp*Rh(dpmp-P, P )](PF6) 3(A), and [{Cp*RhCl2(dpmp-
1.05 (d, JH,H ϭ 7.0 Hz, iPr, 3 H), 1.73 (t, JH,H ϭ 4.0 Hz, Cp*, 15
H), 1.80 (s, p-Me, 3 H), 2.33(sept, JH,H ϭ 7.0 Hz, iPr, 1 H), 2.69
(dt, JH,H ϭ 16.0, JPH ϭ JPH ϭ 12.0 Hz, CH2, 1 H), 3.67 (dt, JH,H ϭ
16.0, JPH ϭ JPH ϭ 12.0 Hz, CH2, 1 H), 4.01 (ddd, JH,H ϭ 16.0,
JPH ϭ 7.0, JPЈH ϭ 4.0 Hz, CH2, 1 H), 4.30 (ddd, JH,H ϭ 16.0,
P, P, P )Au}2](PF6)2 (7). (e) Table S2. Selected bond lengths and
angles for [Cp*2Rh2Cl3(dpmp-P, P, P )](PF6)·CH2Cl2 2(B). (f) Table
S3. Selected bond lengths and angles for [Cp*RhCl(dpmp-
P, P )](PF6) 3(A). (g) Table S4. Selected bond lengths and angles for
[{Cp*RhCl2(dpmp-P, P, P )Au}2](PF6)2 (7). (h) Figure S1. ORTEP
for 2(B). (i) Figure S2. ORTEP for 3(A). (j) Figure S3. ORTEP
for 7.
J
PH ϭ 7.0, JPH ϭ 4.0 Hz, CH2, 1 H), 4.68, 5.20 (AB system, JH,H ϭ
5.5 Hz, p-cymene), 7.0Ϫ8.5 (m, ph, 25 H). 31P{1H} NMR (CDCl3):
δ ϭ Ϫ13.8 (dt, 1JRhP2 ϭ 2JP2P1 ϭ 105, 2JP2P3 ϭ 55.0 Hz, P2), Ϫ10.2
(t, JP1Rh ϭ JP1P2 ϭ 109.0 Hz, P1) and 26.6 (d, JP3P2 ϭ 55.0 Hz,
1
2
2
P3), Ϫ143.5 (sept, JPF ϭ 707.5 Hz, PF6).
Preparation of [{Cp*RhCl2(dpmp-P,P,P)Ag}2](OTf) (4): A mixture
of 1 (52.8 mg, 0.085 mmol), dpmp (107.5 mg, 0.212 mmol) and Ag-
(OTf) (61.4 mg, 0.239 mmol) was stirred in CH2Cl2 (15 mL) and
acetone (10 mL) at room temperature. After 4 h the solvent was
removed and the solids were washed with diethyl ether and the
residue was extracted with CH2Cl2. The CH2Cl2 solution was con-
centrated, and diethyl ether was added to give reddish orange crys-
tals (124.0 mg, 67.5%). UV/Vis (CH2Cl2): λmax ϭ 392 nm. 1H
NMR (CDCl3): δ ϭ 1.25 (d, JH,P ϭ 3.5 Hz, Cp*), 1.90, 2.82, 3.13,
3.48 (m, CH2), 5.32 (s, CH2Cl2), 6.8Ϫ8.2 (m, Ph). The 31P{1H}
Preparation of [{Cp*Rh(µ-Cl)2(dpmp-P,P,P)Cu}2](PF6)2 (8)
(1) One-Pot Synthesis: A mixture of 1 (32.9 mg, 0.053 mmol), dpmp
(60.8 mg, 0.12 mmol) and CuCl (56.1 mg, 0.175 mmol) was stirred
in CH2Cl2 (5 mL) and acetone (5 mL) for 24 h. The solvent was
then removed and the residue extracted with CH2Cl2. The solution
was concentrated to ca. 3 mL and diethyl ether was added, afford-
ing red crystals (47.6 mg, 43.7%).
NMR (CDCl3): δ ϭ 28.6 (JPRh ϭ 146, JP,P ϭ 12.9 Hz, P1), 2.6 (m, (2) From 3: Complex 8 (16.9%) was prepared from 3(A) and CuCl.
the other P nuclei), Ϫ143.6 (sept, JPF ϭ 707.5 Hz, PF6).
UV/Vis (CH2Cl2): λmax ϭ 387, 235 nm. IR (nujol): ν˜ ϭ 835 cmϪ1
.
140
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 134Ϫ142

Homo- and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)rhodium(III)
FULL PAPER
1H NMR (CD2Cl2): δ ϭ 1.10 (d, JH,P ϭ 3.5 Hz), 1.26 (d, JPH
3.5 Hz, Cp*), 2.1Ϫ3.3 (m, CH2), 6.9Ϫ8.05 (c, Ph).
C84H88Cl4Cu2F12P8Rh2·1/2CH2Cl2 (2090.6): calcd. C 48.55, H RhClϪP, P1), Ϫ15.3 (ddd, JRhP2 ϭ 111.1, JP2P1 ϭ 98.0, JP2P3
ϭ
NMR (CDCl3): δ ϭ 28.6 (dd, JRhP3 ϭ 122.2, JP3P2 ϭ 50.1 Hz,
1
2
Rh(CNR)ϪP, P3), Ϫ2.76 (dd, JRhP1 ϭ 113.1, JP2P1 ϭ 98.0 Hz,
1
2
1
2
2
ϭ
4.29; found C 48.52, H 4.25.
50.1 Hz, RhClϪP, P2). C63H68Cl2F6NO6P3Rh2S2 (1483.0): calcd. C
50.02, H 4.62, N 0.94; found C 50.11, H 4.71, N 1.13.
Preparation of [{Cp*Rh(µ-Cl)2(dpmp-P,P,P)Cu}2](BF4)2: The BF4
anion complex (11.1%) was prepared from 1 (0.051 mmol), dpmp
Preparation of [(Cp*RhCl)(dpmp-P,P)]Cl (A): A mixture of [Cp*
(0.011 mmol) and [Cu(MeCN)4](BF4) (0.13 mmol). The complex RhCl2]2 (30.5 mg, 0.049 mmol) and dpmp (55.2 mg, 0.109 mmol)
was established as a BF4 anion analog of 8 by comparison with the
in CH2Cl2 (10 mL) was stirred at room temperature for 24 h. After
the removal of the solvent, the residue was washed with diethyl
ether and crystallized from CH2Cl2 and diethyl ether to give orange
crystals (28.8 mg, 36.0%). FAB MS: m/z ϭ 780 [Mϩ]. UV/Vis
(CH2Cl2): λmax ϭ 356, ca. 270 (sh) nm. 1H NMR (CDCl3): δ ϭ
1.81 (t, J ϭ 3.8 Hz, Cp*, 15 H), 3.47 (m, CH2, 2 H), 4.24 (m, CH2,
1 H), 5.30 (s, CH2Cl2), 5.49 (m, CH2, 1 H), 7.0Ϫ7.7 (c, 25 H).
31P{1H} NMR (CDCl3): δ ϭ Ϫ5.10 ppm (dd, JP3Rh ϭ 115.6,
1H NMR spectrum of 8.
Preparation of [Cp*RhCl(dpmp؍S)](PF6) (9): A mixture of 3(A)
(50.9 mg, 0.055 mmol) and S8 (7.8 mg, 0.030 mmol) was stirred in
CH2Cl2 (5 mL) at room temperature. After 51 h, the solvent was
removed under reduced pressure. After the residue was extracted
with CH2Cl2, the solution was concentrated to ca. 2 mL, and di-
ethyl ether was added, affording a yellow powder (16.7 mg, 31.7%).
UV/Vis (CH2Cl2): λmax ϭ 359, 260 (sh) nm. IR (nujol): ν˜ ϭ 837
J
P2P3 ϭ 99.0 Hz, RhClϪP, P3), Ϫ11.0 (ddd, JP2Rh ϭ 114.1, JP2P3 ϭ
99.0, JP2P1 ϭ 46.5 Hz, RhClϪP, P2), Ϫ29.4 (d, JP1P2 ϭ 46.5 Hz,
CH2P, P1). C42H44Cl2P3Rh·3/4CH2Cl2 (879.2): calcd. C 58.40, H
5.22; found C 58.03, H 5.47. The structure is assumed to be similar
1
cmϪ1 (PF6). FAB MS: m/z ϭ 811 ([M]ϩ). H NMR (CDCl3): δ ϭ
1.64 (t, JH,P1 ϭ JHP2 ϭ 4.0 Hz, Cp*, 15 H), 4.3Ϫ4.9 (m, CH2, 2
H), 6.8Ϫ8.1 (c, Ph, 25 H). 31P{1H} NMR (CDCl3): δ ϭ 35.6 (d,
JP3P2 ϭ 31.5 Hz, P3), 0.92 (dd, JP1Rh ϭ 114.0, JP1P2 ϭ 94.0 Hz,
1
to that of 3(B), based on the H NMR spectrum.
P1), Ϫ15.5 (ddd, JRhP2 ϭ 114.0, JP2P3 ϭ 31.5, JP2P1 ϭ 94.0 Hz, Reaction of 2(A) with Xylyl Isocyanide: A mixture of 2(A) (50 mg,
P2), Ϫ143.6 (sept, JPF ϭ 707.5 Hz, PF6). C42H44ClF6P4RhS
(957.1): calcd. C 49.56, H 4.45; found C 49.71, H 4.53.
0.041 mmol) and xylyl isocyanide (26.9 mg, 0.205 mmol) was
heated to reflux in acetone (15 mL). After 5 h, the solvent was re-
moved and the residue was extracted with CH2Cl2. The solution
was concentrated and diethyl ether was added, affording a dark
brown solid of [Cp*RhCl2(XylNC)] (30 mg, 78%). Workup of the
mother liquor gave 3(A) (10.3 mg, 57.2%).
Preparation of [{Cp*RhCl}(dpmp-P,P,P){RhCl(XylNC)Cp*}](OTf)2
(10): To a mixture of 3(A) (50.6 mg, 0.045 mmol) and Ag(OTf)
(27.4 mg, 0.167 mmol) in CH2Cl2 (10 mL) and acetone (5 mL) was
added XylNC (13.9 mg, 0.107 mmol) at room temperature. After
the reaction mixture was stirred for 24 h usual workup of the mix-
X-ray Data Collection: All complexes were recrystallized from
ture gave orange crystals of 10 (35.2 mg, 52.3%). IR (nujol): ν˜ ϭ CH2Cl2/diethyl ether. The cell constants for 5 were determined
2168 cmϪ1 (NϵC). UV/Vis (CH2Cl2): λmax ϭ 342 nm. 1H NMR
from 20 reflections on a Rigaku four-circle automated dif-
fractometer AFC5S. Data collection was carried out using a Ri-
2
(CDCl3): δ ϭ 1.48 (t, JPH ϭ 4.0 Hz, Cp*, 15 H), 1.56 (d, JPH
ϭ
3.8 Hz, Cp*, 15 H), 2.00 (s, o-Me, 6 H), 4.10 (m, CH2, 1 H), 4.51 gaku AFC5S diffractometer. Intensities were measured by the
(m, CH2, 1 H), 4.90 (m, CH2, 2 H), 6.8Ϫ8.0 (c, 25 H). 31P{1H} 2θϪω scan method using Mo-Kα radiation (λ
ϭ
0.71069).
Table 4. [{Cp*RhCl2(dpmp-P, P, P )Ag}2](OTf)2·H2O (4·H2O), [Cp*Rh(dpmp-P, P, P )](OTf)2 (5), and [{Cp*RhCl2(dpmp-P, P, P )-
Cu}2](OTf)2·2CH2Cl2 (8)
4·H2O[a]
5[b]
8·2CH2Cl2
[a]
Complex
Empirical formula
Formula mass
Crystal system
Space group
C86H88Ag2Cl4F6O7P6Rh2S2
C44H44F6O6P3RhS2
1042.77
triclinic
P1 (no. 2)
12.725(10)
18.23(2)
10.90(1)
99.54(10)
101.70(9)
107.63(6)
2289(3)
2
C86H92Cl8Cu2F12P8Rh2
2217.97
2160.95
orthorhombic
Pccn (no. 46)
31.7839(7)
14.632(3)
19.9580(7)
90
90
90
5648(1)
4
1.546
monoclinic
P21/c (no. 14)
13.573(1)
13.1107(5)
25.2635(6)
90
103.74(2)
90
4227(2)
˚
a /A
˚
b /A
˚
c /A
α /°
β /°
γ /°
V
Z
2
Dcalcd. /gcmϪ3
µ(Mo-Kα) /cmϪ1
2θmax
1.513
6.39
50.0
1.643
12.79
55.0
10.89
55.0
No. measured (unique)
No. observed
No. variable
R; Rw
R1
GOF
10851
8036
10231
5923 [I Ͼ 3.0σ(I)]
523
2864 [I Ͼ 2.0σ(I)]
559
6807 [I Ͼ 3.0σ(I)]
532
0.090; 0.114[c]
0.090(5923 ref)
3.22
0.062; 0.075[c]
0.062
0.155; 0.207[d]
0.074(4155 ref)
2.13
1.09
[a]
[b]
[c]
Measured on a Quantum CCD Rigaku AFC7 instrument.
Measured on a Rigaku AFC5S instrument. R ϭ Σ||Fo2| Ϫ2 |Fc||/Σ|Fo|,
[d] 2 2 2 2 2
Rw ϭ (Σω(|Fo| Ϫ |Fc|)2/ΣωFo ) and R1 ϭ Σ||Fo| Ϫ |Fc||/Σ|Fo| for I Ͼ 3.0σ(I). R ϭ Σ(Fo Ϫ Fc )/ΣFo , Rw ϭ (ΣωFo Ϫ Fc ) /Σω(Fo )]1/2
2 1/2
and R1 ϭ Σ||Fo| Ϫ |Fc|| /Σ|Fo| for I Ͼ 2.0σ(I).
Eur. J. Inorg. Chem. 2004, 134Ϫ142
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
141

Y. Yamamoto et al.
FULL PAPER
Throughout the data collection the intensities of the three standard
reflections were measured after every 200 reflections as a check of
the stability of the crystals and no decay was observed. Absorption
corrections were made using the ψ scan methods.
[1]
A. P. Balch, Homogeneous Catalysis with Metal Phosphane
Complexes (Ed.: L. H. Pignolet). Plenum Press: New York,
1983, p. 167 and references cited therein.
[2]
[3]
T. Tanase, Y. Yamamoto, Trends Organomet. Chem. 1999, 35
The measurements for 4·H2O and 8·2CH2Cl2 were made on an
MSC/ADSC Quantum CCD/Rigaku AFC7 diffractometer, using
Mo-Kα radiation at 0 °C under a cold nitrogen stream. Four pre-
liminary data frames were measured at 0.5° increments of ω in
order to assess the crystal quality and preliminary unit cell param-
eters were calculated. The cell parameters were refined using all
reflections measured in the range 2.8° Ͻ 2θ Ͻ 40°. The intensity
images were measured at 0.5° intervals of ω for a duration of 20 s.
The frame data were integrated using the d*TREK program pack-
age, and the data sets were corrected for absorption using the
REQAB program.
and references cited therein.
H. Suzuki, N. Tajima, K. Tatsumi, Y. Yamamoto, Chem. Com-
mun. 2000, 1801Ϫ1802.
Y. Yamamoto, H. Suzuki, N. Tajima, K. Tatsumi, Chem. Eur.
J. 2002, 8, 372.
Y. Yamamoto, H. Nakamura, J.-F. Ma, J. Organomet. Chem.
2001, 640, 10.
[4]
[5]
[6]
K. K. Klausmeyer, T. B. Rauchfuss, S. R. Wilson, Angew.
Chem. 1998, 110, 1808; Angew. Chem. Int. Ed. 1998, 37, 1694.
S. M. Contakes, K. K. Klausmeyer, R. M. Milberg, S. R. Wil-
son, T. B. Rauchfuss, Organometallics 1998, 17, 3633.
D. J. Darensbourg, W.-Z. Lee, M. J. Adams, D. L. Larkins, J.
H. Reibenspies, Inorg. Chem. 1999, 38, 1378.
S. M. Contakes, K. K. Klausmeyer, T. B. Rauchfuss, Inorg.
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a syn-form. The correct values are δ ϭ 28.1 and 30.1 ppm,
respectively.
Y. Kosaka, Y. Yamamoto, unpublished result.
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Received June 26, 2003
[7]
[8]
The crystal parameters along with the details of the data collections
are summarized in Table 4. Intensities were corrected for Lorentz
and polarization effects. Atomic scattering factors were taken from
[9]
[10]
[11]
the usual tabulation of Cromer and Waber.[22] Anomalous disper-
[23]
sion effects were included in Fcalcd.
;
the values of ∆fЈ and ∆fЈЈ
were those of Creagh and McAuley.[24] All calculations were per-
formed using the teXsan crystallographic software package.[25]
Determination of the Structures: All complexes were solved by di-
rect methods (SIR92) except 7 which was solved by Patterson meth-
ods (DIRDIF94 PATTY) . The non-hydrogen atoms of all com-
plexes were refined anisotropically using full-matrix least-squares
based on F2 or F values. All hydrogen atoms were calculated in
[12]
[13]
[14]
˚
ideal positions with a CϪH distance of 0.95 A. The crystal data
[15]
[16]
are listed in Table 4.
CCDC-190355 for 4·H2O, -213525 for 5 and -190357 for 8·2CH2Cl2
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/
conts/retrieving.html [or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax:
(internat.) ϩ 44-1223-336-033; E-mail: deposit@ccdc.cam.ac.uk].
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
Acknowledgments
The authors would like to thank Professor Shigetoshi Takahashi
and Dr Fumie Takei of The Institute of Scientific and Industrial
Research, Osaka University for performing the FAB mass spec-
trometry measurements. This work was partially supported by a
Grant-in Aid for Scientific Research from the Ministry of Edu-
cation, Science, Culture and Sports, Japan.
[25]
Early View Article
Published Online October 23, 2003
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Eur. J. Inorg. Chem. 2004, 134Ϫ142