Homo- and heteronuclear complexes based on arene ruthenium complexes bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)

Article abstract of DOI:10.1016/j.ica.2003.10.018

Reactions of [(p-cymene)RuCl₂]₂ (1a) with dpmp ((Ph₂PCH₂)₂PPh) in the absence or presence of KPF₆ afforded the ionic complexes [{(p-cymene)RuCl ₂}(dpmp-P¹, P³; P²){RuCl(p-cymene)}] (X) (2a₁: X = Cl; 2a₂: X = PF₆). A (p-cymene)RuCl moiety constructs a 6-membered ring coordinated by two terminal P atoms of the dpmp ligand and another one binds to a central P atom of the ligand. Reactions of [(C₆Me₆)RuCl₂] ₂ (1b) with an excess of dpmp in the presence of KPF₆ gave a 4-membered complex [(C₆Me₆)RuCl(dpmp-P ¹, P²)](PF₆) (3b), chelated by a terminal and a central P atom and another terminal atom is free. Use of Ag(OTf) instead of KPF₆ gave [{(C₆Me₆)RuCl₂(dpmp)Ag} ₂](OTf)₂ (5b) that the Ag atoms were coordinated by a terminal and a central P atom of each dpmp ligand. Reaction with an equivalent of dpmp in the presence of KPF₆ gave [{(C₆Me ₆)RuCl}(dpmp-P¹, P²; P³){(C ₆Me₆)RuCl₂}](PF₆) 4b. Complex has a structure that the (C₆Me₆)RuCl₂ moiety coordinated to the free P atom of 3b. Complex 3b was treated with MCl ₂(cod) (M = Pd, Pt), [Pd(MesNC)₄](PF₆) ₂ (MesNC = 2,4,6-Me₃C₆H₂NC) or [Pt₂(XylNC)₆](PF₆)₂ (XylNC = 2,6-Me₂C₆H₃NC), generating [{(C ₆Me₆)RuCl(dpmp)}₂MCl₂](PF ₆)₂ (8b: M = Pd; 9b: M = Pt), [{(C₆Me ₆)RuCl(dpmp)}₂{Pt(MesNC)₂}](PF ₆)₄ (10b) and [{(C₆Me₆)RuCl(dpmp)} ₂{Pt₂(XylNC)₄}](PF₆)₄ (11b), respectively. Complex 3b reacted readily with [Cp*MCl ₂]₂ (M = Rh, Ir) or AuCl(SC₄H₈), affording the corresponding hetero-binuclear complexes [{(C₆Me ₆)RuCl}(dpmp-P¹, P²; P³)(MCl ₂Cp*](PF₆) (6b: M = Rh; 7b: M = Ir) and [{(C ₆Me₆)RuCl}(dpmp-P¹, P²; P ³)(AuCl)](PF₆) (12b). These complexes have two chiral centers. Some complexes were separated as two diastereomers by successive recrystallization. The structures of 3b, 5b, 6b, 8b and 12b were confirmed by X-ray analyses.

Full text of DOI:10.1016/j.ica.2003.10.018

Inorganica Chimica Acta 357 (2004) 1270–1282
www.elsevier.com/locate/ica
Homo- and heteronuclear complexes based on arene
ruthenium complexes bearing
bis(diphenylphosphinomethyl)phenylphosphine (dpmp) q
a
a
a
Yasuhiro Yamamoto a,*,1, Yuichi Sinozuka , Yoshihiro Tsutsumi , Kei Fuse ,
b
Katsuaki Kuge , Yusuke Sunada , Kazuyuki Tatsumi
b
b
a
Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan
b
Research Center for Materials Science and Department of Chemistry, Graduate School of Science,
Nagoya Uiversity, Furo-cho, Chikusa-ku, Nagoya 454-8602, Japan
Received 21 October 2003; accepted 25 October 2003
Abstract
Reactions of [(p-cymene)RuCl2]2 (1a) with dpmp ((Ph2PCH2)2PPh) in the absence or presence of KPF6 afforded the ionic complexes
[{(p-cymene)RuCl2}(dpmp-P1; P3; P2){RuCl(p-cymene)}](X) (2a1: X ¼ Cl; 2a2: X ¼ PF6). A (p-cymene)RuCl moiety constructs a 6-
membered ring coordinated by two terminal P atoms of the dpmp ligand and another one binds to a central P atom of the ligand.
Reactions of [(C6Me6)RuCl2]2 (1b) with an excess of dpmp in the presence of KPF6 gave a 4-membered complex [(C6Me6)RuCl(dpmp-
P1; P2)](PF6) (3b), chelated by a terminal and a central P atom and another terminal atom is free. Use of Ag(OTf) instead of KPF6 gave
[{(C6Me6)RuCl2(dpmp)Ag} 2](OTf)2 (5b) that the Ag atoms were coordinated by a terminal and a central P atom of each dpmp ligand.
Reaction with an equivalent of dpmp in the presence of KPF6 gave [{(C6Me6)RuCl}(dpmp-P1; P2; P3){(C6Me6)RuCl2}](PF6) 4b.
Complex has a structure that the (C6Me6)RuCl2 moiety coordinated to the free P atom of 3b. Complex 3b was treated with MCl2(cod)
(M ¼ Pd, Pt), [Pd(MesNC)4](PF6)2 (MesNC ¼ 2,4,6-Me3C6H2NC) or [Pt2(XylNC)6](PF6)2 (XylNC ¼ 2,6-Me2C6H3NC), generat-
ing [{(C6Me6)RuCl(dpmp)}2MCl2](PF6)2 (8b: M ¼ Pd; 9b: M ¼ Pt), [{(C6Me6)RuCl(dpmp)}2{Pt(MesNC)2}](PF6)4 (10b) and
[{(C6Me6)RuCl(dpmp)}2{Pt2(XylNC)4}](PF6)4 (11b), respectively. Complex 3b reacted readily with [Cp*MCl2]2 (M ¼ Rh, Ir) or
AuCl(SC4H8), affording the corresponding hetero-binuclear complexes [{(C6Me6)RuCl}(dpmp-P1; P2; P3)(MCl2Cpꢀ](PF6) (6b:
M ¼ Rh; 7b: M ¼ Ir) and [{(C6Me6)RuCl}(dpmp-P1; P2; P3)(AuCl)](PF6) (12b). These complexes have two chiral centers. Some
complexes were separated as two diastereomers by successive recrystallization. The structures of 3b, 5b, 6b, 8b and 12b were confirmed
by X-ray analyses.
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: (Arene)ruthenium complex; Bis(diphenylphosphinomethyl)phenylphosphine (dpmp); Heteronuclear complex; Pentamethylcyclopenta-
dienylrhodium (iridium); Group 11 metal
1. Introduction
dination behaviors for bi- and mononuclear metal cen-
ters, and linear coordination mode for trinuclear metal
centers. The chemistry on rhodium, iridium, gold and
silver has been widely developed [1]. We have systemati-
cally explored the chemistry of palladium and platinum
bearing dpmp and isocyanide ligands and the prepara-
tions of hetero-nuclear complexes based on their palla-
dium and platinum complexes [2,3]. These complexes
bearing the dpmp ligand have been essentially con-
structed by the square planar frameworks. The chemistry
of dpmp for octahedral or quasi-octahedral complexes
The bis(diphenylphosphinomethyl)phenylphosphine
(dpmp) ligand has versatile bridging and chelating coor-
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.ica.2003.10.018.
* Corresponding author. Tel.: +0668798456; fax: +0668798459.
E-mail addresses: yamamo24@sanken.osaka-u.ac.jp (Y. Yamam-
oto).
1
Present address: The Institute of Scientific and Industrial Research,
Osaka University. Fax: +81-52-789-2943.
0020-1693/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2003.10.018

Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
1271
has attracted our attention. This configuration could be
expected to lead to the formation of complexes with di-
verse dimensionality. Recently,s we reported that the re-
actions of dpmp with [Cp*RhCl2]2 in the presence of
KPF6 gave the mononuclear or binuclear complexes,
[Cp*RhCl(dpmp)](PF6) and [{Cp*RhCl2(dpmp)RhCl2
Cp}*](PF6) that the dpmp ligand acts as a bidentate one,
depending on the reaction conditions [4,5]. Since the
former complex has a free P nucleus, it can act as a pre-
cursor that led to the formation of the hetero-nuclear
complexes. Use of Ag(OTf) instead of KPF6 gave a
hetero-tetranuclear complex [{Cp*RhCl2(dpmp)Ag}2]
(OTf)2. Our interests shifted to the ruthenium complexes
that three sites of quasi-octahedral geometry were occu-
pied by an arene ligand. We wish to describe herein the
preparation of mono- and binuclear ruthenium com-
plexes, and the transformation to the hetero tri- and tet-
ranuclear ones based on the ruthenium complexes. Part of
this paper has already been briefly reported [4].
from an elemental analysis. The molecular peak of 1084
corresponds to [molecular peak-Cl + 1]þ in the FAB
mass spectroscopy. The 1H NMR spectrum showed two
doublets at d 0.72 and 0.87 with a 1:1 intensity ratio for
methyl protons of isopropyl groups. The 31P{1H} NMR
spectrum showed the presence of two kinds of phos-
phorus nuclei; a doublet at d 24.1 and a triplet at d
)40.6. These results coincided with the ionic structure
that a (p-cymene)RuCl moiety is coordinated by two
terminal P atoms and another one binds to a central P
atom. The ionic structure was confirmed by the fact that
the NMR spectral data of [(p-cymene)RuCl(dpmp-
P1; P3; P2)RuCl2(p-cymene)](PF6) (2a2), generated by a
similar reaction in the presence of KPF6, are in close
similarity with that of 2a1. In the UV–Vis spectra in
CH2Cl2, the highest wavelength of 2a1 appeared at kmax
369 nm and that of 2a2 appeared at kmax ca. 380 nm.
The blue shift of 2a1 probably depends on stabilization
of a HOMO level arising from a weak interaction
between the cationic molecule and the Cl anion. An
attempt to prepare a mononuclear complex was unsuc-
cessful; the reaction with an excess of dpmp was carried
out in the presence of KPF6, generating 2a2 exclusively
(Scheme 1).
2. Results and discussion
2.1. Preparation of mono- and binuclear complexes
Hexamethylbenzene complex (1b) reacted readily
with an excess of dpmp in the presence of KPF6, giving
two kinds of complexes (3b(A) and 3b(B)) with the
empirical formula of [(C6Me6)RuCl(dpmp)](PF6)
The p-cymene complex (1a) was treated with dpmp in
a 1:1 molar ratio, affording orange compound (2a1) with
the empirical formula of [{(p-cymene)RuCl2}2(dpmp)]
Scheme 1. Reactions of [(arene)RuCl2]2 (1) with dpmp in the absence or presence of KPF6 or Ag(OTf).

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Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
Scheme 2. Stereochemistry of mono- and binuclear complexes; the PF6 anion was omitted for clarity.
1
(Scheme 2). In the H NMR spectrum of the reaction
mixture, the relative population of the two diastereo-
mers was found to be 2:1 for 3b(A) and 3b(B). These
complexes were separated by fractional recrystallization.
Iodide analogs of 3b(A) and 3b(B), [(C6Me6)RuI(dpmp-
P1; P2)](PF6) (3b1(A) and 3b1(B)), were prepared by a
similar reaction of [(C6Me6)RuI2]2 with dpmp in the
presence of KPF6. The H NMR spectrum of the reac-
tion mixture was found to be 2.5:1 for a relative popu-
lation of 3b1(A) and 3b1(B).
It was confirmed by X-ray analyses of 3b(A) and
3b1(A) that the molecular structures consist of a 4-
membered ring that the (C6Me6)Ru moiety was coor-
dinated by the terminal P1 and the central P2 atoms and
a halogen atom, and another terminal P3 atom was free
(Figs. 1 and 2). These compounds have two chiral cen-
ters at the Ru and P2 atoms. Based on the priority order
of the ligands [4], both complexes are the diastereomers
with a RRuSP2/SRuRP2 pair, in which we designate them
as an anti-form (anti-3b or anti-3b1), since the halogen
atom sits at a trans-position to the P-substituted phenyl
group. Thus, the other diastereomers (3b(B) or 3b1(B))
with a RRuRP2/SRuSP2 pair are designated as syn-3b or
syn-3b1.
1
In the separate experiments, the H NMR spectra of
the reaction mixtures of 3b or 3b1 were measured after 7
days, and the intensity ratios remained still constant,
suggesting that the two diastereomers are not intercon-
vertible at room temperature. Based on the formation
ratio, the anti-form prefers to the syn-form.
The other arene complex such as 1,2,3,5-Me4C6H2 (1c)
reacted readily with an excess of dpmp in the presence of
KPF6, giving the complex (3c), [(1,2,3,5-Me4C6H2)
RuCl(dpmp-P1; P2)](PF6). The separation of diastereo-
mers was not made.
1
Fig. 1. Molecular structure of anti-3b; the PF6 anion and CH2Cl2 were
omitted for clarity.
Fig. 2. Molecular structure of anti-3b1; the PF6 anion was omitted for
clarity.

Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
1273
The reaction of 1b with an equivalent of dpmp in the
presence of KPF6 generated two kinds of diastereomers
4b(A) and 4b(B), [(C6Me6)2Ru2Cl3(dpmp-P1; P2; P3)]
(PF6). The H NMR spectrum of the reaction mixture
1
showed two sets of arene protons, indicating the pres-
ence of two isomers consisting of the ratio of ca. 1.3:1.
Two diastereomers were separated by successive re-
crystallization and were not interconvertible as 3. In the
1H NMR spectra, the arene protons appeared at d 1.63
and 1.97 for 4b(A) and at d 1.63 and 1.82 for 4b(B). The
31P{1H} NMR spectrum of 4b(A) showed two doublets
at d )0.07 (d, 2JP1P2 ¼ 92.0 Hz, P1) and 29.3 (d, 2JP3P2
¼
50.0 Hz, P3) and a double doublet at d )5.41 (dd,
2JP2P1 ¼ 92.0 Hz, 2JP2P3 ¼ 50.0 Hz, P2), assignable to the
P1, P3 and P2 nucleus, respectively. In 31P{1H} NMR
spectrum of 4b(B), two doublets due to the P1 and P3
Fig. 3. Molecular structure of 5b; the OTf anions were omitted for
clarity.
2
nuclei appeared at d )2.16 (d, JP1P2 ¼ 88.5 Hz, P1) and
27.1 (d, 2JP3P2 ¼ 50.0 Hz, P3), respectively, and a double
dated by X-ray analysis (Fig. 3). The complex isolated as
crystals is a kind of diastereomer. A similar heteronuclear
complex, [{Cp*RhCl2(dpmp)Ag}2](OTf)2, has been ob-
tained in the reaction of [Cp*RhCl2]2 and an excess of
dpmp with Ag(OTf) [4,5].
doublet due to a P2 nucleus appeared at d )0.49 (dd,
2
2JP2P1 ¼ 88.5 Hz, JP2P3 ¼ 50.0 Hz, P2).
In order to confirm the stereochemistry of 4b, anti-3b
was treated with 1b in a 2:1 molar ratio, giving 4b(A), in
comparison with the 1H and 31P{1H} NMR spectra.
Since the reaction proceeds with retention, we can assign
4b(A) to the anti-form (anti-4b) with a RRuRP/SRuSP
pair and the other diastereomer (4b(B)) to the syn-form
(syn-4b) with a RRuSP/SRuRP pair on the basis of the
priority order of the ligands. Thus, the stereochemistry
between anti-3b and 4b(A), or syn-3b and 4b(B) is sim-
ilar. Analogous type of mono- and binuclear rhodium
complexes has been prepared from [Cp*RhCl2]2, dpmp
and KPF6 [4,5].
Reactions of anti-3b or syn-3b with [Cp*RhCl2]2 oc-
curredreadily,generatingorangecomplexesformulatedas
[(C6Me6)RuCl(dpmp-P1; P3; P2)RhCl2Cp*](PF6) (anti-
6bandsyn-6b)basedonanelementalanalysis, respectively
(Scheme 4). The FAB mass spectrometry indicated the
molecular peak of m=z 1114 for syn-6b, corresponding to
the value of a cationic molecule. The crystals of syn-6 were
suitable for X-ray analysis. The stereochemistry of the
starting complex was remained (Fig. 4). In the 1H NMR
spectra, the Cp* and arene protons appeared at d 1.27 and
1.85 for anti-6b and at d 1.26 and 2.02 for syn-6b, respec-
tively. A similar reaction of syn-3b with [Cp*IrCl2]2 also
gave syn-7b, [(C6Me6) RuCl(dpmp-P1; P3; P2) IrCl2
Cp*](PF6), with a RRuRP/SRuSP pair, since the reaction
proceeds with retention.
Reaction of anti-4b with xylyl isocyanide (XylNC) at
room temperature led to an elimination of the Cp*RuCl2
fragment, generating anti-3b and (C6Me6)RuCl2(Xy-
lNC), suggesting stability of
(Scheme 3).
a 4-membered ring
In the 31P{1H} NMR spectrum of 4b, 6b and 7b, the
chemical shift of the P3 nucleus bound to the Cp*MCl2
(M ¼ Rh, Ir) or (C6Me6)RuCl2 moiety appeared at d ca.
28 for M ¼ Rh and Ru, and at d ca. 2 for M ¼ Ir. A
similar trend that the chemical shift of the iridium
complexes appeared at a higher magnetic field than
those found in the ruthenium and rhodium ones has
been observed for [LMCl(BDMPP-P,O)] and [LM
(TDMPP-P,O,O)] (LM ¼ (arene)Ru [6], Cp*Rh [7]
or Cp*Ir [8]; BDMPP-P,O ¼ PPh(2,6-(MeO)2C6H3)
2.2. Preparation of heteronuclear complexes
When 1b was treated with dpmp in a 1:2 molar ratio in
the presence of Ag(OTf) instead of KPF6, an orange
complex (5b) formulated as a dimeric complex [{(C6Me6)
RuCl2(dpmp)Ag}2](OTf)2 was obtained, on the basis of
FAB mass spectrometry. The molecular peak is m/z 2045,
corresponding to the value of [{(C6Me6)RuCl2(dpmp)
Ag}2](OTf) (wt. 2046). The detailed structure was eluci-
Scheme 3. Reaction of anti-4b with xylyl isocyanide (XylNC); the PF6 anion was omitted for clarity.

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Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
Scheme 4. Reactions of 3b with various metal complexes; the PF6 or OTf anions were omitted for clarity.
Treatment of anti-3b with PdCl2(cod) or PtCl2(cod) in
a 2:1 molar ratio gave yellow complexes formulated as
[{(C6Me6)RuCl(dpmp)}2MCl2](PF6)2 (8b: M ¼ Pd; 9b:
M ¼ Pt). In the 1H NMR spectra of these complexes the
arene protons appeared at d 1.84 as a singlet, suggesting a
symmetric structure. In fact the X-ray analysis of 8b re-
vealed that the PdCl2 group binds two (C6Me6)RuCl
(dppm) moieties that are located mutually at the trans-
positions (Fig. 5). Since the reaction proceeded stereo-
specifically, 9b is also assumed to be an anti-form.
The 31P{1H} NMR spectrum of anti-8b indicated a
singlet at d 9.00 and two doublets at d 5.49 and )0.86 for
dpmp ligands, assignable to the P3, P1 and P2 nuclei,
respectively. This result showed that there are no cou-
plings between the central P2 atom and the terminal P3
one, whereas in the platinum complex (anti-9b), three
resonances for the P1, P2, and P3 nuclei appeared at d
2.83 (2JP1P2 ¼ 87.7 Hz) as a doublet, at d 1.53
Fig. 4. Molecular structure of syn-6b; the PF6 anion was omitted for
clarity.
(2-O-6-MeOC6H3) or TDMPP-P,O,O ¼ P{2,6-(MeO)2
C6H3} (2-O-6-MeOC6H3)2, depending on the higher elec-
tron density on the Ir metal than for the Ru or Rh metal.
2
(2JP2P1 ¼ 87.5 Hz, JP2P3 ¼ 48.5 Hz) as a double doublet

Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
1275
AuCl}2](PF6)2 bearing an Au–Au bond has been isolated
[10]. These results suggest that the reactions occur with
delicate balance between the metals and ligands. There is
no information on difference of reactivity at present.
2.3. Crystal structures
2.3.1. Structures of anti-3b and anti-3b1
Perspective drawings with the atomic numbering
scheme are given in Figs. 1 and 2, and selected bond
lengths and angles are listed in Tables 1 and 2. Complex
(anti-3b) contains one CH2Cl2 solvate molecule and has
two half PF6 moieties, one with the P atom on an in-
version center and the other with the P atom on a 2-fold
axis. The (C6Me6)Ru moiety is surrounded by halogen
and the terminal and central P atoms of the dpmp ligand
and another terminal P atom is free. The molecular
structures of both complexes are fundamentally similar
to that of the rhodium complex, [Cp*RhCl(dpmp)](PF6)
Fig. 5. Molecular structure of 8b; the PF6 anions were omitted for
clarity.
2
and at d 5.83 (1JP3Pt ¼ 3712 Hz, JP3P2 ¼ 48.5 Hz) as a
double doublet, respectively; the latter was accompanied
by satellite peaks due to 195Pt nucleus.
When anti-3b was treated with [Pd(MesNC)4](PF6)2
(MesNC ¼ 2,4,6-Me3C6H2NC), orange complex (10b)
formulated as [{(C6Me6)RuCl(dpmp)}2 {Pd(MesNC)2}]
(PF6)2 was isolated. The IR spectrum showed a sharp
band at 2197 cmꢁ1, reminiscent of terminal isocyanide
ꢀ
ꢀ
[4]. The Ru-I length of 2.686(2) A is longer by ca. 0.29 A
than that of Ru–Cl bond length and the average Ru–P
length of anti-3b1 is longer than that of anti-3b. They are
the results of great covalent radii and steric bulkiness of
iodide ion. The P–Ru–P bite angles of 71.4° are com-
pared with that of the Rh analog [4].
1
ligands. The H NMR spectrum showed three charac-
teristic singlets at d 1.48, 1.54 and 1.87 with an intensity
ratio of 1:2:3, assignable to p-, m- and arene methyl pro-
tons, respectively, suggesting a symmetric structure. The
similar complex was generated by the reaction of 8b with
mesityl isocyanide in the presence of KPF6. Reaction with
a binuclear platinum complex [Pt2(RNC)6](PF6)2 (R ¼
2,6-Me2C6H3) gave yellow crystals formulated as
[{(C6Me6)RuCl(dpmp)}2{Pt2(RNC)4}](PF6)4 (11b) from
the elemental analysis. The atomic ratio of Pt and Ru
atoms was estimated to be 1:1 from the fluorescent X-ray
spectrometry. The IR spectrum showed a m (NBC) band
at 2162 cmꢁ1. The 1H NMR spectrum showed two sing-
lets at d 1.54 and 1.88 due to the arene and o-methyl
protons, respectively. Since the binuclear complexes of
platinum and palladium, [M2(RNC)6](PF6)2 (M ¼ Pd, Pt)
reacted readily with various tertiary phosphines, afford-
ing [Pt2(CNR)4(PR3)2](PF6)2 that tertiary phosphines sat
at the axial positions [9], 11b is assumed to have the mo-
lecular structure that two (C6Me6)RuCl(dpmp) moieties
occupy the axial positions of the dimeric platinum iso-
cyanide complex.
Complexes (anti-3b and anti-3b1) reacted readily with
AuCl(C4H8S), generating the corresponding complexes
[(C6Me6)RuX(dpmp)AuCl](PF6) (anti-12b: X ¼ Cl; anti-
12b1: X ¼ I). The FAB mass spectrometry is m=z 1036 for
the former and m/z 1129 for the latter, corresponding to
the values of the cationic molecules. The X-ray analysis of
anti-12b revealed that the reaction proceeds stereospe-
cifically. Reaction of [Cp*RhCl(dpmp-P1; P2)](PF6) with
AuCl(SC4H8) generated the tetranuclear complex,
[{Cp*RhCl2(dpmp)Au}2](PF6)2 like 5b, whereas in the
reaction with an iridium complex [Cp*IrCl(dpmp-
P1; P2)](PF6), a dimeric complex, [{Cp*IrCl(dpmp)
2.3.2. Structure of 5b
A perspective drawing with the atomic numbering
scheme is given in Fig. 3, and selected bond lengths and
angles are listed in Table 3. X-ray analysis revealed that
the molecule has a crystallographically imposed inversion
center in the middle of the Ag ꢂ Ag* vector like that of
[{Cp*RhCl2(dpmp)Ag}2] [5] and each (C6Me6)RuCl2
moiety is connected by a terminal P atom of dpmp li-
ꢀ
gands. The Ag ꢂ Cl separations (2.80–2.82 A) are longer
than those found in the Ag–Cl bridged bonds to be sig-
nificant bonding between Ag and Cl atoms [11]. However,
in the cubane-like cluster [MoAg3S3Cl][PPh3]3O [12] and
the [Ag2Cl4]2ꢁ anion in [AsPh4]2[Ag2Cl4] [13], the Ag–
Clbridging bond lengths are in the very wide range of
ꢀ
ꢀ
2.446(2)–2.843(4) A (2.792(4)–2.843(4) A for the former
ꢀ
and 2.446(2)–2.809(2) A for the latter). Based on these
results, there is likely a weak interaction between the Ag
and Cl atoms. 2 The Cl(1)–Ag(1)–Cl(2) angle of 72.21(6)°
is narrower by approximately 13° than that in [{Cp*
RhCl2(dpmp-P,P,P)Cu}2](PF6)2, resulting in the long
Ag–Cl bond lengths in comparison with the Cu–Cl length
ꢀ
(2.443(2) and 2.568(2) A).
Each of two central P atoms is the chiral center. The
priority order of the ligands is Ag > Ph > C2 > C1 for the
2
In [5], we have reported that in the complex [{Cp*RhCl2(dpmp-
ꢀ
P,P,P)Ag}2], the Ag ꢂ ꢂ ꢂ Cl separations of 2.709 and 2.911 A is too
longer to have any Ag–Clbridging bond, the former length, however, is in
the range of the Ag–Clbridging interaction, and the Ag atoms are
assumed to be three-coordinate.

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Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
Table 1
Selected bond lengths and angles for [{(C6Me6)RuCl}(dpmp-P1; P2)](PF6) ꢂ CH2Cl2 (anti-3b)
Ru(1)–Cl(1)
P(1)–C(1)
P(3)–C(2)
2.4004(8)
1.850(3)
1.839(4)
84.33(3)
96.3(1)
Ru(1)–P(1)
P(2)–C(1)
2.3057(8)
1.834(3)
Ru(1)–P(2)
P(2)–C(2)
2.3342(8)
1.835(3)
Cl(1)–Ru(1)–P(1)
Ru(1)–P(1)–C(1)
Ru(1)–P(2)–C(2)
Cl(1)–Rh(1)–P(2)
P(1)–C(1)–P(2)
P(2)–C(2)–P(3)
83.72(3)
94.7(2)
112.8(2)
P(1)–Ru(1)–P(2)
Ru(1)–P(2)–C(1)
71.45(3)
95.8(1)
119.2(1)
Table 2
Selected bond lengths and angles for [{(C6Me6)RuI}(dpmp-P1; P2)](PF6) (anti-3b1)
Ru(1)–I(1)
P(1)–C(43)
P(3)–C(44)
2.686(2)
1.85(2)
1.85(2)
84.7(1)
96.1(6)
95.4(6)
Ru(1)–P(1)
P(2)–C(43)
2.331(5)
1.86(2)
Ru–P(2)
P(2)–C(44)
2.340(5)
1.82(2)
I(1)–Ru(1)–P(1)
Ru(1)–P(1)–C(43)
Ru(1)–P(2)–C(43)
I(1)–Ru(1)–P(2)
P(1)–C(43)–P(2)
Ru–P(2)–C(44)
85.8(1)
94.4(9)
123.6(6)
P(1)–Ru(1)–P(2)
P(2)–C(44)–P(3)
71.3(2)
111.1(9)
Table 3
Selected bond lengths and angles for [{(C6Me6)RuCl2(dpmp-P)Ag}2](OTf)2 (5b)
Ag(1)–P(2)
Ru(1)–Cl(1)
2.438(2)
2.428(2)
1.856(8)
1.850(9)
2.804(3)
144.81(8)
85.25(8)
109.8(3)
113.6(3)
72.21(6)
Ag(1)–P(3)*
Ru(1)–Cl(2)
P(2)–C(13)
2.399(3)
2.435(2)
1.837(9)
Ru(1)–P(1)
P(2)–C(20)
2.356(2)
1.850(9)
P(1)–C(13)
P(3)–C(20)
Ag(1)–Cl(1)
Ag(1)–Cl(1)
2.819(2)
85.89(8)
119.8(3)
114.4(3)
P(2)–Ag(1)–P(3)*
Cl(2)–Ru(1)–P(1)
Ag(1)–P(2)–C(13)
Ag(1)*–P(3)–C(20)
Cl(1)–Ag(1)–Cl(2)
Cl(1)–Ru(1)–Cl(2)
Rh(1)–P(1)–C(13)
Ag(1)–P(2)–C(20)
Cl(1)–Ru(1)–P(1)
P(1)–C(13)–P(2)
P(2)–C(20)–P(3)
87.31(7)
121.8(5)
110.0(5)
central P2 and P2ꢀatoms, where C1 is a methylene car-
bon atom between the P1 and P2 atoms, and C2 atom is
a methylene carbon atom between the P2 and P3 atoms.
Complex has been identified as the RPꢀ2SP2/SP2RPꢀ2
pair. The Ag(2)P(4)C(2) eight-ring adopts a chair form.
The angles around the Ru atom consisting of the P and
two Cl atoms are in the range 85.3–87.3°, and are
somewhat narrower than that (87.8–90.5°) in the Rh
analog [5]. The P(2)–Ag–P(3)* angle of 144.81(8)° is
narrower than that (149.5(2)°) for the Rh analog. The
Ru–Cl and Ru–P bond lengths are longer than those
are compared with those in [Cp*RhCl(dpmp)RhCl2
Cp*](PF6) [4].
2.3.4. Structure of 8b
A perspective drawing with the atomic numbering
scheme is given in Fig. 5, and selected bond lengths and
angles are listed in Table 5. The molecule has a crystal-
lographically imposed inversion center on the Pd atom
and each (C6Me6)RuCl(dpmp) moiety coordinated to a
Pd atom at the trans-positions. The molecular structure
has the four-chiral centers at two Ru atoms and two
central P atoms. Stereochemistry is the anti-form. The
bond angles and lengths around the Ru metal are similar
to those found in the complexes bearing the
(C6Me6)RuCl(dpmp) moiety. The geometry around the
ꢀ
found in anti-3b. The Ag(1)–P(2) length of 2.438(2) A is
ꢀ
longer than the Ag(1)–P(3)* length of 2.399(3) A. They
are probably responsible for release of crowdness
around the Ru atoms.
ꢀ
Pd atom is square planar. The Pd–Cl length of 2.305(2) A
ꢀ
and the Pd–P bond lengths of 2.351(2) A are typical.
2.3.3. Structure of syn-6b
A perspective drawing with the atomic numbering
scheme is given in Fig. 4, and selected bond lengths and
angles are listed in Table 4. The angles and lengths
around the Ru atom are similar to those for anti-3b. The
angles around the Rh atoms are near 90°. The average
2.3.5. Structure of 12b
Since the molecular structure has been briefly de-
scribed in the previous communication [4], the detail is
not described. The P(3)–Au–Cl(2) angle is 172.10(9)°,
ꢀ
ꢀ
Rh–Cl length of 2.412 A and the Rh–P length of 2.333 A

Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
1277
Table 4
Selected bond lengths and angles for [{(C6Me6)RuCl}(dpmp-P) (RhCl2Cp)](PF6) (6b)
Rh(1)–Cl(1)
Ru(1)–Cl(3)
2.419(4)
2.388(4)
1.82(2)
Rh(1)–Cl(2)
Ru(1)–P(2)
P(2)–C(23)
2.404(5)
2.320(5)
1.83(2)
Rh(1)–P(1)
Ru(1)–P(3)
P(2)–C(30)
2.333(4)
2.314(5)
1.86(2)
P(1)–C(23)
P(3)–C(30)
1.85(2)
90.2(2)
Cl(1)–Rh(1)–Cl(2)
Cl(3)–Ru(1)–P(2)
Rh(1)–P(1)–C(23)
P(2)–C(30)–P(3)
Cl(1)–Rh(1)–P(1)
Cl(3)–Ru(1)–P(3)
P(1)–C(23)–P(2)
86.7(1)
83.1(2)
126.3(8)
Cl(2)–Rh(1)–P(1)
P(2)–Ru(1)–P(3)
Ru(1)–P(2)–C(23)
91.6(1)
71.6(2)
118.0(5)
82.3(2)
109.7(5)
94.0(8)
Table 5
Selected bond lengths and angles for [{(C6Me6)RuCl(dpmp-P1; P2)}{ PdCl2}](PF6) (8b)
Pd(1)–Cl(2)
Ru(1)–P(1)
2.305(2)
2.350(2)
1.827(7)
1.862(6)
180.0
Pd(1)–P(3)
Ru(1)–P(2)
P(2)–C(1)
2.351(2)
2.316(2)
1.849(7)
Ru(1)–Cl(1)
P(1)–C(1)
P(2)–C(2)
2.394(2)
1.838(6)
1.834(6)
P(1)–C(3)
P(3)–C(2)
Cl(2)–Pd(1)–Cl(2)*
P(3)–Pd(1)–P(3)*
Cl(1)–Ru(1)–P(2)
P(1)–C(1)–P(2)
P(2)–C(2)–P(3)
Cl(2)–Pd(1)–P(3)
Pd(1)–P(3)–C(2)
P(1)–Ru(1)–P(2)
Ru(1)–P(2)–C(1)
88.19(6)
116.1(2)
71.69(6)
95.5(2)
Cl(2)–Pd(1)–P(3)
Cl(1)–Ru(1)–P(1)
Ru(1)–P(1)–C(1)
Ru(1)–P(2)–C(2)
91.81(6)
83.26(6)
94.7(2)
180.0
84.05(6)
95.6(3)
121.9(3)
116.6(2)
1
near a linear array. The Au–Cl(2) and Au(1)–P(3)
ꢀ
lengths are 2.297(2) and 2.245(2) A, respectively. These
values are compared with those found in the dimeric
complex [{Cp*IrCl(dpmp)AuCl}2](PF6)2 [10].
mass: m=z 1084 ([M + 1]þ) (M ¼ cationic molecule). H
NMR (CDCl3): d 0.72 (d, JHH ¼ 7.0 Hz, MeCH, 6H), 0.87
(d, JHH ¼ 7.0 Hz, MeCH, 6H), 1.71 (s, Me, 6H), 2.45 (sep.,
CH, JHH ¼ 7.0 Hz, 2H), 2.80 (d, 2JHH ¼ 7.5 Hz, CH2, 1H),
2.87 (d, 2JHH ¼ 7.5 Hz, CH2, 1H), 3.10 (d, 2JHH ¼ 7.5 Hz,
2
CH2, 1H), 3.18 (d, JHH ¼ 7.5 Hz, CH2, 1H), 4.89 (AB
system, d, 2JHH ¼ 5.5 Hz, C6H4, 2H), 4.97 (AB system, d,
2JHH ¼ 5.5 Hz, C6H4, 2H), 5.03 (AB system, d, 2JHH ¼ 5.5
Hz, C6H4, 2H), 5.17 (AB system, d, 2JHH ¼ 5.5 Hz, C6H4,
2H), 5.27 (s, CH2Cl2), 6.4–8.4 (c, Ph, 25H). 31P{1H}
3. Experimental
3.1. General considerations
2
All reactions were performed under a nitrogen atmo-
sphere. Methylene chloride was distilled from CaH2 and
diethyl ether was distilled from LiAlH4. Bis(diphenyl-
phosphinomethyl)phenylphosphine [14], [(arene)RuCl2]2
(arene ¼ p-cymene [15], C6Me6[16]), [Cp*RhCl2]2 [17],
[Cp*IrCl2]2 [8], AuCl(SC4H8) [18] and [Pt2(XylNC)6]
(PF6) [20] were prepared according to the literature. The
infrared and electronic absorption spectra were recorded
on FT/IR-5300 and U-best 30 instruments, respectively.
1H NMR spectra were measured on a JEOL EPC400 in-
strument at 400 MHz and 31P{1H} NMR spectra were
measured at 161 MHz using 85% H3PO4 as an external
reference.
NMR (CDCl3): d 24.1 (d, JPP ¼ 30.1 Hz), )40.6 (t,
2JPP ¼ 30.1 Hz). Anal. Calcd for C52H57P3Cl 4Ru2 ꢂ 2CH2
Cl2: C, 50.33; H, 4.77. Found: C, 50.96; H, 4.83%.
3.3. Preparation of [{(p-cymene)RuCl2}(dpmp-P1,P3;
P2){RuCl(p-cymene)}](PF6) (2a2)
A mixture of 1a (102.2 mg, 0.167 mmol), dpmp (100.6
mg, 0.199 mmol) and KPF6 (41.1 mg, 0.223 mmol) was
stirred in CH2Cl2 (10 ml) and acetone (10 ml) at room
temperature. After 12 h, the solvent was removed to
dryness, the residue was washed with diethyl ether and
extracted with CH2Cl2. The CH2Cl2 solution was con-
centrated to ca. 3 ml and diethyl ether was added, giving
reddish brown compound 2a2 (148.4 mg, 70.3%).
IR(nujol): 837 cmꢁ1 (PF6). UV–Vis (CH2Cl2): kmax ca.
3.2. Preparation of [{(p-cymene)RuCl2}(dpmp-P1,P3;
P2)RuCl(p-cymene)]Cl (2a1)
1
2
380 nm. H NMR (CDCl3): d0:72 (d, JHH ¼ 7.0 Hz,
2
A mixture of [(p-cymene)RuCl2]2 (84.1 mg, 0.13 mmol)
and dpmp (70.5 mg, 0.13 mmol) in CH2Cl2 (20 ml) was
stirred at room temperature for 3 h. The solution was
concentrated and diethyl ether was added, giving orange
crystals of 2a1 (123.7 mg, 79.6%). IR (nujol): 835 cmꢁ1
(PF6). UV–Vis (CH2Cl2): kmax 369, 230(sh) nm. FAB
MeCH, 6H), 0.88 (d, JHH ¼ 7.0 Hz, Me CH, 6H), 1.72
2
(s, Me, 6H), 2.47 (sep., d, JHH ¼ 7.0 Hz, MeCH, CH,
2H), 2.96 (b, CH2, 2H), 3.23 (b, CH2, 2H), 4.91 (AB
2
system, d, JHH ¼ 5.8 Hz, C6H4, 2H), 4.99 (AB system,
2
2
d, JHH ¼ 5.8 Hz, C6H4, 2H), 5.04 (d, JHH ¼ 5.8 Hz,
C6H4, 2H), 5.20 (d, 2JHH ¼ 5.8 Hz, C6H4, 2H), 6.55–7.67

1278
Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
2
(c, 25H). 31P{1H} NMR (CDCl3): d 24.1 (d, JPP ¼ 30.5
(dt, 2JHH ¼ 9.5 Hz, 2JHP ¼ 2JHP ¼ 6.0 Hz, CH2, 1H), 4.84
2
2
2
Hz, terminal P), )40.6 (t, JPP ¼ 30.5 Hz, central P),
(ddd, JHH ¼ 16 Hz, JHP ¼ 2JHP ¼ 10 Hz, 1H) 7.0–7.8
1
)143.8 (sep., JPF ¼ 707.5 Hz, PF6). Anal. Calcd. for
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d 0.46 (d,
2
C52H57P3Cl3F6Ru2: C, 50.84; H, 4.68. Found: C, 51.14;
H, 4.73%.
2JP1P2 ¼ 85.0 Hz, P1), )9.59 (dd, JP2P1 ¼ 85.0 Hz,
2
JP2P3 ¼ 47.5 Hz, P2), )22.8 (d, JP3P2 ¼ 47.5 Hz, P3),
1
)143.8 (sep., JPF ¼ 713 Hz, PF6). syn-3b1: 1H
3.4. Preparation of [(C6Me6)RuCl(dpmp-P1,P2)](PF6)
(3b)
NMR(CDCl3): d 2.07 (s, Me, 18H), 3.23 (dd, 2JHH ¼ 6.5
2
2
Hz, JHP ¼ 5.0 Hz, 1H), 3.63 (dd, JHH ¼ 6.0 Hz,
2JHP ¼ 4.5 Hz, CH2, 1H), 3.92 (dt, JHH ¼ 9.5 Hz,
2
A mixture of [(C6Me6)RuCl2]2(34.2 mg, 0.051 mmol),
dpmp (67.0 mg, 0.132 mmol) and KPF6 (24.1 mg, 0.132
mmol) was stirred in CH2Cl2 (10 ml) and acetone (10
ml) at room temperature. After 4 h, the solvent was
removed and the residue was extracted with CH2Cl2.
The solution was concentrated and diethyl ether was
added, giving yellow crystals (59.2 mg, 61.1%) of 3b. The
relative population between anti-3b and syn-3b in the
reaction mixture is 2:1. Two diastereomers were sepa-
rated by successive recrystallization of 3b from CH2Cl2
and diethyl ether. UV–Vis (CH2Cl2): kmax 328 nm. FAB
mass: m=z 804 ([M ) 2]þ), 642 ([M–C6Me6-2]þ)
(M ¼ cationic molecule). anti-3b ( ¼ 3b(A)): 1H NMR
2JHP ¼ 2JHP ¼ 6.0 Hz, CH2, 1H), 4.59 (dt, 2JHH ¼ 9.5 Hz,
2JHP ¼ 2JHP ¼ 10 Hz, CH2, 1H), 6.8–7.8 (m, Ph, 25H).
31P{1H} NMR (CDCl3): d 6.13 (d, 2JP1P2 ¼ 43.4 Hz, P1),
)11.2 (dd, 2JP2P1 ¼ 43.5 Hz, 2JP2P3 ¼ 87.0 Hz, P2), )29.8
(d, JP3P2 ¼ 43.5 Hz, P3), )145.6 (sep., JPF ¼ 713 Hz,
PF6). Anal. Calcd. for C44H47P4F6 IRu: C, 50.73; H,
4.55. Found: C, 50.28; H, 4.52%.
2
1
3.6. Preparation of [(1,2,3,5-Me4C6H2) RuCl(dpmp-
P1,P2)](PF6) (3c)
Similarly to the preparation of 3b except the reaction
time of 2 days, brown complex (3c) (33.7 mg, 55%) was
obtained by a mixture of [(1,2,3,5-Me4C6H2)RuCl2]2
(30.3 mg, 0.0495 mmol), dpmp (29.9 mg, 0.059 mmol) and
KPF6 (13.2 mg, 0.072 mmol). IR (nujol): 839 cmꢁ1 (PF6).
UV–Vis (CH2Cl2): kmax 380 nm. FAB mass: m=z 1083
([M]þ) (M ¼ cationic part). Anal. Calcd. for C52H57P4Cl3
2
(CDCl3): d 1.93 (s, Me, 18H), 2.84 (dd, JHH ¼ 15.0 Hz,
2JHP ¼ 6.0 Hz, CH2, 1H), 3.66 (dd, JHH ¼ 15.0 Hz,
2
2JHP ¼ 9.5 Hz, CH2, 1H), 3.93 (dt, JHH ¼ 16.0 Hz,
2
2
2JHP ¼ JHP ¼ 12.0 Hz, CH2, 1H), 4.42 (dt, JHH ¼ 16.0
Hz, JHP ¼ 2JHP ¼ 10.0 Hz, CH2, 1H), 7.0–7.6 (m, Ph,
2
25H). 31P{1H} NMR (CDCl3): d 6.08 (d, JP1P2 ¼ 90.0
2
2
2
F6Ru2 ꢂ 1/2CH2Cl2: C, 49.62; H, 4.62. Found: C, 49.49; H,
Hz, P1),)2.70 (dd, JP2P1 ¼ 90.0 Hz, JP2P3 ¼ 50.5 Hz,
2
4.75%. A: 31P{1H} NMR (CDCl3): d )0.02 (d, JP1P2
¼
2
P2), )24.2 (d, JP3P2 ¼ 50.5 Hz, P3), )143.8 (sep.,
92.7 Hz, P1),a)3.67 (dd, JP2P1 ¼ 97.2 Hz, JP2P3 ¼ 51.8
2
2
1JPF ¼ 707.5 Hz, PF6). syn-3b ( ¼ 3b(B)): 1H NMR
Hz, P2),a 24.1 (d, JP2P3 ¼ 51.8 Hz, P3),a)145.6 (sep.,
2
2
(CDCl3): d 2.06 (s, Me, 18H), 3.00 (dd, JHH ¼ 15.0 Hz,
1JPF ¼ 713 Hz, PF6). B: d )0.55 (2JP1P2 ¼ 102 Hz,
2JHP ¼ 8.5 Hz, CH2, 1H), 3.29 (dd, JHH ¼ 15.0 Hz,
P1),b)5.14 (dd, JP2P3 ¼ 50.2 Hz, JP2P1 ¼ 102 Hz,
2
2
2
JHP ¼ 5.5 Hz, CH2, 1H), 4.23 (dt, JHH ¼ 15.0 Hz,
P2),b28.4 (d, JP2P1 ¼ 50.2 Hz, P3),b)145.6 (sep, JPF
2
1
2JHP ¼ 2JHP ¼ 13.0 Hz, H), 4.99 (c, CH2, 1H), 7.0–7.7
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d 5.50 (d,
¼ 713 Hz, PF6).
2JP1P2 ¼ 93.0 Hz, P1),3.87 (dd, JP2P1 ¼ 93.0 Hz,
2
3.7. Preparation of [{(C6Me6)RuCl}2(dpmp-P1,P2;
P3)](PF6) (4b)
2JP2P3 ¼ 45.0 Hz, P2), )30.2 (d, JP3P2 ¼ 45.0 Hz, P3),
2
1
)143.8 (sep., JPF ¼ 707.5 Hz, PF6). Anal. Calcd. for
C44H47P4ClF6Ru: C, 55.61; H, 4.99; Found: C, 54.61;
H, 4.97%.
Similarly to the preparation of 3b, yellow crystals
(62.2 mg, 61%) of 4b were obtained from a mixture of 1b
(53.0 mg, 0.079 mmol), dpmp (40.5 mg, 0.080 mmol)
and KPF6 (24.9 mg, 0.135 mmol). Similarly to 3.3, each
diastereomer was isolated by successive recrystallization
of 4b. The relative population of the reaction mixture:
4b(A) : 4b(B) ¼ 1.3:1. IR(nujol): 841 cmꢁ1 (PF6). UV–
Vis (CH2Cl2): kmax 371, 327 nm. Anal. Calcd. for
C54H61P4Cl3F6Ru2: C 51.14, H 5.01. Found: C 51.09, H
5.06%. anti-4b ( ¼ 4b(A)):1H NMR (CDCl3): d 1.63 (s,
3.5. Preparation of [(C6Me6)RuI(dpmp-P1,P2)](PF6)
(3b1)
Similarly to the preparation of 3b, brown crystals of
3b1 (114.8 mg, 63.0%) were prepared by the reaction of
[(C6Me6)RuI2]2(90.5 mg, 0.0875 mmol) with dpmp (96.5
mg, 0.191 mmol) in the presence of KPF6 (45.3 mg,
0.246 mmol). A relative population of 3b1(A) ( ¼ anti-
3b1) and 3b1(B) ( ¼ syn-3b1) is 2.5:1. Two diastereomers
were separated by successive recrystallization from
2
Me, 18H), 1.97 (s, Me, 18H), 2.68 (dt, JHH ¼ 16.0 Hz,
2
2JHP ¼ 2JHP ¼ 10.5 Hz, CH2, 1H), 3.59 (dt, JHH ¼ 16.0
2
Hz, JHP ¼ 2JHP ¼ 11.0 Hz, CH2, 1H), 3.88 (ddd,
CH2Cl2 and diethyl ether. anti-3b1. IR(nujol): 837 cmꢁ1
.
2
2
2JHH ¼ 16.0 Hz, JHP ¼ 6.0 Hz, JHP ¼ 4.0 Hz, CH2,
1
anti-3b1 ( ¼ 3b1(A)): H NMR(CDCl3): d 2.07 (s, Me,
1H), 4.21 (dt, JHH ¼ 16.0 Hz, JHP ¼ 2JHP ¼ 7.00 Hz,
2
2
2
2
18H), 2.97 (dd, JHH ¼ 6.0 Hz, JHP ¼ 4.8 Hz, 1H), 4.21
CH2, 1H)), 6.9–7.8 (m, Ph, 25H). 31P{1H} NMR
(dt, JHH ¼ 16 Hz, JHP ¼ 2JHP ¼ 12 Hz, CH2, 1H), 4.73
2
2

Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
1279
2
(CDCl3): d 29.3 (d, JP3P2 ¼ 50.0 Hz, P3),)0.07 (d,
3.76 (m, CH2, 1H), 4.16 (m, CH2, 2H), 5.0 (dt,
2JHH ¼ 16.5 Hz, 2JHP ¼ 2JHP ¼ 7.0 Hz CH2, 1H), 7.0–8.2
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d 27.3 (dd,
2JP1P2 ¼ 92.0 Hz, P1), )5.41 (dd, JP2P1 ¼ 92.0 Hz,
2
2JP2P3 ¼ 50.0 Hz, P2), )143.8 (sep., JPF ¼ 707.5 Hz,
1
1
2
PF6). syn-4b ( ¼ 4b(B)): H NMR (CDCl3): d 1.65 (s,
2JP3Rh ¼ 142.7 Hz, JP3P2 ¼ 53.5 Hz, P3), 3.28 (d,
2
Me, 18H), 1.82 (s, Me, 18H), 3.51 (m, CH2, 1H), 3.72
(m, CH2, 1H), 4.12 (m, CH2, 1H), 4.79 (m, CH2, 1H),
6.8–7.8 (c, Ph, 25H). 31P{1H} NMR (CDCl3): d 27.1 (d,
2JP1P2 ¼ 91.0 Hz, P1), )0.62 (dd, JP2P1 ¼ 91.0 Hz,
2JP2P3 ¼ 53.5 Hz, P2), )143.8 (sep., 1JPF ¼ 711.5 Hz, PF6).
2JP3P2 ¼ 50.0Hz, P3), )2.16 (d, JP1P2 ¼ 88.5 Hz, P1),
3.10. Preparation of [{(C6Me6) RuCl(dpmp-P1,P2;
P3)IrCl2Cp}](PF6)2 (syn-7b ¼ 7b(B))
2
)0.49 (dd, 2JP2P1 ¼ 88.5 Hz, 2JP2P3 ¼ 50.0Hz, P2), )143.8
1
(sep., JPF ¼ 707.5 Hz, PF6).
Similarly to the preparation of (6b), yellow complex
(46.7 mg, %) was prepared from syn-3b (49.3 mg, 0.052
mmol) and [Cp*IrCl2]2 (21.1 mg, 0.027 mmol). IR(nu-
jol): 837 cmꢁ1. UV–Vis (CH2Cl2): kmax 333 nm. FAB
mass: m=z 1222 ([M + 1]þ) (M ¼ cationic molecule).1H
NMR(CDCl3): d 1.26 (d, JHP ¼ 2.0 Hz, Cp*, 15H), 2.03
3.8. Preparation of [{(C6Me6) RuCl2Ag(dpmp-P1,P2,
P3)}2](OTf)2 (5b)
A mixture of 1b (51.3 mg, 0.077 mmol), dpmp (88.1
mg, 0.172 mmol) and AgOTf (52.0 mg, 0.202 mmol) was
stirred in CH2Cl2 (10 ml) and acetone (10 ml) at room
temperature. After 4 days, the solvent was removed and
the residue was extracted with CH2Cl2. Removal of the
solvent and recrystallization of the residue from CH2Cl2
and diethyl ether gave orange crystals (108.0 mg, 64%)
of 5b. FAB mass: m/z 2045 ([M + OTf ) 1]þ) (M ¼ cat-
ionic molecule). UV(CH2Cl2): kmax 365 nm. 1H
NMR(CD2Cl2): d 1.63 (s, Me, 36H), 2.57, 2.88, 3.33 (c,
CH2), 6.75–8.1 (m, Ph, 50H). 31P{1H} NMR (CD2Cl2):
d )3.0 (c, P), 0.58 (c, P), 4.0 (c, P). Anal. Calcd. for
C90H94Ag2Cl4F6O6P6Ru2S2: C, 49.37; H, 4.33. Found:
C, 49.24; H, 4.32%.
2
(s, Me, 18H), 2.85 (dt, JHH ¼ 16.0 Hz, JHP ¼ 10.8 Hz,
2
2
CH2, 1H), 3.66 (dt, JHH ¼ 16.0 Hz, JHP ¼ 12.0 Hz,
2
2
CH2, 1H), 4.31 (ddd, JHH ¼ 16.0 Hz, JHP ¼ 7.5 Hz,
2JHP ¼ 4.5 Hz, CH2, H), 4.50 (ddd, JHH ¼ 16.0 Hz,
2
2JHP ¼ 10.0 Hz, JHP ¼ 6.0 Hz, CH2, 1H), 5.27 (s,
2
CH2Cl2), 6.9–7.7 (m, Ph, 25H). 31P{1H} NMR (CDCl3):
d 2.01 (d, 2JP3P2 ¼ 49.5 Hz, P3), 0.32 (d, 2JP1P2 ¼ 93.0 Hz,
P1), )5.81 (dd, JP2P3 ¼ 93.0 Hz, JP2P3 ¼ 49.5 Hz, P2),
2
2
1
)143.8 (sep., JPF ¼ 711.4 Hz, PF6). Anal. Calcd. for
C54H62Cl3F6IrP4Ru ꢂ 1/2CH2Cl2: C, 47.06; H, 4.56.
Found: C, 46.59; H, 4.55%.
3.11. Preparation of [{(C6Me6) Ru(dpmp-P1,P2;
3.9. Preparation of [{(C6Me6) RuCl}(dpmp-P1,P2;
P3)RhCl2Cp*](PF6) (6b)
P3)}2(PdCl2)](PF )2 (8b)
6
A mixture of anti-3b (31.0 mg, 0.033 mmol) and
PdCl2(cod) (5.8 mg, 0.020 mmol) was stirred in CH2Cl2
(15 ml) at room temperature. After 10h, the solvent was
concentrated to ca. 3 ml and diethyl ether was added to
form yellow crystals (32.4 mg, 94.5%). IR(nujol): 839
cmꢁ1 (PF6). UV(CH2Cl2): kmax 348 nm. FAB mass: m=z
804 ([M–PdCl2-2]þ), 642 ([M–PdCl2–C6Me6-2]þ)
A mixture of syn-3b (56.3 mg, 0.0592 mmol) and
[Cp*RhCl2]2(18.4 mg, 0.0298 mmol) in CH2Cl2 (10 ml)
and acetone (5 ml) was stirred at room temperature for 20
h. After removal of the solvent, the residue was washed
with diethyl ether. The residue was recrystallized from
CH2Cl2 and diethyl ether, giving yellow crystals of syn-6b
( ¼ 6b(B)) (30.2 mg, 41%). IR(nujol): 641 cmꢁ1 (PF6).
UV–Vis (CH2Cl2): kmax 401 nm. FAB mass: m=z 1114
([M]þ) (M ¼ cationic molecule). 1H NMR (CDCl3): d
1.26 (d, JHP ¼ 3.5 Hz, Cp*, 15H), 2.02 (s, Me, 18H), 2.86
(dt, JHH ¼ 15.5 Hz, JHP ¼ JHH ¼ 10.5 Hz CH2, 1H), 3.64
1
(M ¼ cationic molecule). H NMR- (CDCl3): d 1.84 (s,
2
2
Me, 36H), 3.30 (dt, JHH ¼ 16 Hz, JHP ¼ 2JHP ¼ 10 Hz,
H), 3.58 d(t, JHH ¼ 16 Hz, JHP ¼ 2JHP ¼ 112.4 Hz,
CH2, H), 3.58 (c, CH2, H), 4.59 (c, CH2, H), 6.8–7.8 (m,
Ph, 50H). 31P{1H} NMR (CDCl3): d 9.00 (s, P3), 5.49
(d, 2JP1P2 ¼ 83.2 Hz, P1), )0.86 (d, 2JP1P2 ¼ 83.2 Hz, P2),
2
2
2
2
(dt, JHH ¼ 15.5 Hz, JHP ¼ 2JHH ¼ 12.5 Hz CH2, 1H),
1
4.20 (ddd, 2JHH ¼ 16.5 Hz, 2JHP ¼ 6.5 Hz, 2JHP ¼ 3.8 Hz
)144.1 (sep., JPF ¼ 704 Hz, PF6). Anal. Calcd. for
2
2
CH2, 1H), 4.44 (dt, JHH ¼ 16.5 Hz, JHP ¼ 2JHH ¼ 8.8
Hz, 2JHH ¼ 5.3 Hz CH2, 1H), 5.27 (s, CH2Cl2), 7.0–7.75
(m, Ph, 25H). 31P{1H} NMR (CDCl3): d 29.3 (dd,
C88H94Cl4- F12P8PdRu2: C, 50.57; H, 4.80. Found: C,
50.87; H, 4.56%.
2JP3Rh ¼ 137.5 Hz, JP3P2 ¼ 50.5 Hz, P3), 4.04 (dd,
3.12. Preparation of [{(C6Me6) RuCl(dpmp-P1,P2;
P3)}2PtCl2](PF6)2 (9b)
2
2
2JP2P1 ¼ 94.5 Hz, JP2P3 ¼ 50.5 Hz, P2), 0.24 (d,
2JP1P2 ¼ 94.5 Hz, P1), )143.8 (sep., JPF ¼ 711.5 Hz).
1
Anal. Calcd. for C52H62Cl4F6P3RhRu ꢂ 1/2CH2Cl2: C,
50.28; H, 4.8. Found: C, 50.64; H, 4.97%. Similarly to the
preparation of 6b(B), anti-6b ( ¼ 6b(A)) (55%) was ob-
tained from anti-3b and [Cp*RhCl2]2. 1H NMR (CDCl3):
Similarly to the preparation of 8b, orange complex
(17.3 mg, 39%) was prepared from [{(C6Me6)RuCl
(dpmp)}](PF6) (39.4 mg, 0.042 mmol) and PtCl2(cod) (9.5
mg, 0.025 mmol) in CH2Cl2 (15 ml) for 20h. IR(nujol):
1
1
d 1.27 (d, JHP ¼ 3.5 Hz, Cp*, 15H), 1.85 (s, Me, 18H),
839 (PF6) cmꢁ1. UV(CH2Cl2): kmax 330 nm. H NMR

1280
Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
(CD2Cl2): d 1.84 (s, Me, 36H), 2.64, 3.70, 4.24 (c, CH2),
6.65–7.6 (m, Ph, 50H). 31P{1H} NMR (CD2Cl2): d 5.81
(dt, 1JPPt ¼ 3712 Hz, 2JP3P2 ¼ 48.5 Hz, P3), 2.83 (d, 2JP1P2
Hz, CH2, H), 7.0–7.75 (m, Ph, 25H). 31P{1H} NMR
2
(CD2Cl2): d 18.3 (d, JP1P2 ¼ 25.0 Hz, P1), 6.91 (d,
2
2JP3P2 ¼ 87.0 Hz, P3), )4.97 (dd, JP2P3 ¼ 87.0 Hz,
¼ 87.5 Hz, P1), 1.53 (dd, JP2P1 ¼ 87.5 Hz, JP2P3 ¼ 48.5
Hz, P2), )143.8 (sep, 1JPF ¼ 708 Hz, PF6). Anal. Calcd. for
C88H94Cl4F12P8PtRu2: C, 48.79; H, 4.34. Found: C,
48.15; H, 4.69%.
2JP2P1 ¼ 25.0 Hz, P2), )143.8 (sep., 1JPF ¼ 707.5 Hz, PF6).
Anal. Calcd. for C44H47AuCl2F6P4Ru: C 44.68, H 4.01;
Found: C 44.09, H 4.12%.
2
2
3.16. Preparation of [(C6Me6) RuI(dpmp-P1,P2;
P3)AuCl](PF6) (anti-12b1 ¼ 12b1(A))
3.13. Preparation of [{(C6Me6) Ru(dpmp-P1,P2;
P3)}2{Pd(MesNC)2}](PF6)2 (10b)
Similarly to the preparation of 6b, brown complex anti-
12b1 (34.6 mg, 46%) was generated from anti-3b1 (61.0
mg, 0.0586 mmol) and AuCl(SC4H8) (18.9 mg, 0.059
mmol). FAB mass: m/z 1129 ([M ) 1]þ) (M ¼ cationic
molecule). IR(nujol): 841 (PF6) cmꢁ1. 1H NMR (CDCl3):
d 2.07 (s, Me, 18H), 3.44 (m, CH2, 1H), 4.63 (m, CH2, 1H),
4.78 (m, CH2, 1H), 5.35 (m, CH2, 1H), 6.9–7.7 (m, Ph,
25H). 31P{1H} NMR (CDCl3): d 21.0 (d, J3PP2 ¼ 22.8 Hz,
P3), 2.04 (d, JP1P2 ¼ 80.0 Hz, P1), )13.5 (dd, JP2P1 ¼ 80.0
A mixture of anti-3b (33.5 mg, 0.0353 mmol),
PdCl2(MesNC)2 (8.6 mg, 0.0184 mmol) and KPF6 was
stirred in CH2Cl2 (10 ml) and acetone (10 ml) at room
temperature for 16 h. The solvent was removed and the
residue was extracted with CH2Cl2. After removal of the
solvent, the residue was washed with diethyl ether and
recrystallized from CH2Cl2 and diethyl ether, giving
orange complex of 10b (28.8 mg, 63%). IR(nujol): 2197
(NBC), 839 (PF6) cmꢁ1. UV(CH2Cl2): kmax 365 nm. 1H
NMR(CD2Cl2): d 1.48 (s, 4-Me, 6H), 1.54 (s, 2-Me,
12H), 1.87 (s, arene Me, 36H), 3.4–5.4 (c, CH2, 8H), 6.70
(s, 3-H, 4H), 7.0–7.7 (m, Ph, 50H). Anal. Calcd. for
1
Hz, JP2P3 ¼ 22.8 Hz, P2), )143.8 (sep., JPF ¼ 707.5 Hz,
PF6). Anal. Calcd. for C44H47AuCl2F6IP4Ru ꢂ CH2Cl2: C
39.77, H 3.63; Found: C 39.55, H 3.69%.
C108H116Cl2F24N2P10PdRu2: C, 50.14; H, 4.52; N, 1.08.
Found: C, 50.91; H, 4.95; N, 1.08%.
3.17. X-ray crystallography – data collection
Cell constants of anti-3b1( ¼ 3b1(A)) were determined
from 20 reflections on a Rigaku AFC5S diffractometer.
Intensity measurements were measured by the 2h–x scan
3.14. Preparation of [{(C6Me6) RuCl(dpmp-P1,P2;
P3)}2{Pt2(XylNC) }](PF6)4 (11b)
4
ꢀ
method using MoKa radiation (k ¼ 0:71069 A).
Similarly to the preparation of 10b, orange complex
11b (21.0 mg, 42%) was prepared by a mixture of anti-3b
(30.5 mg, 0.032 mmol) and [Pt2(XylNC)6](PF6) (23.5
Throughout the data collection the intensities of the
three standard reflections were measured every 200 re-
flections as a check of the stability of the crystals and no
decay was observed. Absorption corrections were made
with w scans. Other complexes were set on a Quantum
CCD/Rigaku AFC7 diffractometer. Intensity measure-
ments were made by using Mo Ka radiation
2
mg, 0.016 mmol). IR(nujol): 2162 (N@C), 839 (PF6)
1
cmꢁ1. UV(CH2Cl2): kmax 333 nm. H NMR(CD2Cl2): d
1.54 (s, Me, 36H), 1.88 (s, o-Me, 24H), 3.39 (m, CH2,
2H), 3.93 (m, CH2, 2H), 4.13 (m, CH2, 2H), 4.83 (m,
CH2, 2H), 6.8–7.7 (m, Ph, 62H). Fluorescent X-ray
analysis: Ru:Pt:Cl:P ¼ 1: (1.1–1.2): 1.3–1.4): (6.0–6.2).
ꢀ
(k ¼ 0:71069 A) at )80 °C for anti-3b and at 20 °C for
four other complexes under a cold nitrogen stream.
Four preliminary data frames were measured at 0.5°
increments of x, in order to assess the crystal quality
and preliminary unit cell parameters were calculated.
The cell parameters were refined using all of the reflec-
tions measured in the range 2.8° < 2h < 56°. The in-
tensity images were measured at 0.5° intervals of x for a
duration of 20 s. The frame data were integrated using a
d*TREK program package and the data sets were cor-
rected for absorption using a REQAB program. The
crystal parameters along with data collections are sum-
marized in Table 6. Intensities were collected for Lorenz
and polarization effects. Atomic scattering factors
were taken from the usual tabulation of Cromer and
Waber [20]. Anomalous dispersion effects were included
in Fcalc [21]; the values of Df 0 and Df 00 were those,
Creagh and McAuley [22]. All calculations were per-
formed using the teXsan crystallographic software
package [23].
Anal. Calcd. for
2CH2Cl2: C, 47.50; H, 4.19; N, 1.78. Found: C, 47.35;
H, 4.17; N, 1.77.
C
124H130Cl2F24N4P10Pt2Ru2 ꢂ 1/
3.15. Preparation of [(C6Me6) RuCl(dpmp-P1,P2;
P3)AuCl](PF6) (anti-12b ¼ 12b(A))
Similarly to the preparation of 6b except the reaction
time of 15 h, yellow crystals of anti-12b (45.8 mg, 91%)
were prepared by a mixture of anti-3b (40.5 mg, 0.0426
mmol) and AuCl(SC4H8) (18.0 mg, 0.056 mmol). FAB
mass: m/z 1036 ([M ) 2]þ) (M ¼ cationic molecule).
IR(nujol): 835 (PF6) cmꢁ1. UV(CH2Cl2): kmax 341 nm. 1H
NMR (CD2Cl2): d 1.93 (s, Me, 18H), 3.14 (ddd,
JHH ¼ 16.0 Hz, JHP ¼ 8.0 Hz, JHP ¼ 10.0 Hz, CH2, H),
2
2
2
4.21 (ddd, JHH ¼ 16.0 Hz, JHP ¼ 12.0 Hz, JHP ¼ 12.0
Hz, CH2, H), 4.84 (dt, 2JHH ¼ 16.0 Hz, 2JHP ¼ 2JHP ¼ 10.0
Hz, CH2, H), 4.57 (dt, JHH ¼ 16 Hz, JHP ¼ 2JHP ¼ 8.0
2
2

Table 6
Crystallographic data for [(C6Me6)RuCl(dpmp-P1; P2)](PF6)CH2Cl2 anti-3b, [(C6Me6)RuI(dpmp-P1; P2)](PF6) anti-3b1, [{(C6Me6)RuCl2(dpmp-P1; P2; P3)Ag}2](PF6)2 (5b), [{(C6Me6)
RuCl}(dpmp-P1; P2; P3)(RhCl2Cp)](PF6) (6b) and [{(C6Me6)RuCl(dpmp-P1; P2; P3)}2(PdCl2)](PF6)2 (8b)
Complex
Formula
anti-3b
C45H49Cl3F6P4Ru
anti-3b1
C44H47F6IP4Ru
5b
6b
C54H62Cl3F6P4RhRu
8b
C90H98Cl8F12P8PdRu2
C90H94Ag2Cl4F6O6
P6Ru2S2
2195.37
Molecular weight
Crystal system
Space group
1035.2
1041.72
1259.30
2247.70
monoclinic
C2=c
(number 15)
monoclinic
P21=n
(number 14)
triclinic
ꢁ
monoclinic
P21=n
(number 14)
monoclinic
P21=c
(number 14)
P1
(number 2)
Lattice parameters
a
b
c
a
22.805(1)
12.2283(9)
12.810(4)
17.930(3)
19.487(2)
90.0
12.577(3)
14.073(2)
15.302(1)
115.526(4)
98.902(4)
103.641(5)
2271.1(7)
2
18.388(4)
9.6660(4)
33.884(2)
90.0
9.625(4)
18.745(4)
25.292(2)
90.0
33.558(2)
90.0
b
c
V
Z
103.229(2)
90.0
9109(1)
102.33(1)
90.0
97.181(3)
90.0
95.200(1)
90.0
4372(1)
4
1.582
5975(1)
4
1.400
4544(2)
4
1.643
8
1.509
7.17
Dcalc (g/cm3)
1.605
10.83
l(Mo Ka) (cmꢁ1
Scan rate (minꢁ1
2hmax
)
)
12.68
16
8.21
19.41
–
55.0
–
55.6
–
56.4
–
55.3
50.0
7693
Number of reflections measured (unique)
Number of reflections observed
13 729
13 074
10 255
5884
13 673
5688 [I > 3:0rðIÞ]
9562
6942 [I > 2:0rðIÞ]
3623 [I > 3:0rðIÞ]
[I> 2:0rðIÞ]
[I > 3:0rðIÞ]
532
Number of variables
a
535
0.072, 0.068
255
535
547
R; Rw
0.080, 0.112
0.080 (3924 reflections)
1.48
0.067, 0.082
0.067
2.09
0.110, 0.147
0.110
2.31
0.081, 0.094
0.081
2.10
R1
0.057 (10 781 reflections)
2.96
Goodness of fitb
P
P
P
2
2 1=2
a R ¼ kFoj ꢁ jFck= jFoj and Rw ¼ ½ wðjFoj ꢁ jFcjÞ =wjFoj ꢃ ðw ¼ 1=r2ðFoÞÞ.
P
2
1=2
b GOF ¼ ½ wðjFoj ꢁ jFcjÞ =ðNo ꢁ NpÞꢃ
.

1282
Y. Yamamoto et al. / Inorganica Chimica Acta 357 (2004) 1270–1282
3.18. Determination of the structure
Research, Osaka University for measurements of FAB
mass spectroscopy. This work was partially supported
by a Grant-in Aid for Scientific Research from the
ministry of Education, Science, Culture, and Sports,
Japan (12640545).
The structures of complexes except anti-3b, anti-3b1
and 8b solved by direct methods, were solved by Patt-
erson methods (DIRDIF92 PATTY) and refined on F
values. The positions of all non-hydrogen atoms except
the C and F atoms, refined isotropically in anti-3b1, were
refined with anisotropic thermal parameters by using
full-matrix least-squares methods. All hydrogen atoms
were calculated at the ideal positions with the C–H
References
ꢀ
distance of 0.97 A.
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[2] (a) T. Tanase, Y. Yamamoto, Trends Organomet. Chem. (1999)
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4. Conclusion
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In this paper the chemistry of dpmp has been ex-
tended from the square planar complexes to the oc-
tahedral ones. In the reactions of [(arene)RuCl2]2 with
dpmp, complexes bearing the anti-form were generated
preferentially for the mono- and binuclear complexes.
Based on the priority of the ligands around the chiral
centers at the Ru and central P atoms, the anti-form
of the mono-nuclear complex has a RRhSP2/SRhRP2
pair and that of binuclear complexes has a RRhRP2/
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5. Supplementary materials
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Tables listing detailed crystallographic data, atomic
positional parameters, and bond lengths and angles are
available from the authors upon request. CCDC:
217678, 217679, 217680, 217681, 2217682 and 202044
for anti-3b, anti-3b1, 5b, 6b, 8b and 12b, respectively.
Crystal data (Table 1S), selected bond lengths and an-
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also available as supplementary material.
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Acknowledgements
We thank Professor Shigetoshi Takahashi and Dr.
Fumie Takei of The Institute of Scientific and Industrial