Synthesis of novel heterotetrametallic (d6-d10-d8) polyalkynyl complexes starting from heterobimetallic chloride-bridged (d6-d8) compounds

Article abstract of DOI:10.1002/1099-0682(200106)2001:6<1631::AID-EJIC1631>3.0.CO;2-6

The reaction between the half-sandwich cyclopentadienyl complexes [M(η⁵-C₅Me₅)Cl₂(PEt ₃)] (M = Rh, Ir) and [cis-M′(C₆F₅)₂(thf)₂] (M′ = Pt, Pd; thf = tetrahydrofuran) affords the corresponding chloride-bridged heterobinuclear Rh,Ir/Pt,Pd complexes [(PEt₃)(η⁵-C₅Me₅)M(μ-Cl) ₂M′(C₆F₅)₂] (1-4). In contrast, similar reactions with the chloro-bridged binuclear compounds [{M(η⁵-C₅Me₅)Cl(μ-Cl)}₂] (M = Rh, Ir) lead instead to the unexpected mixed salt complexes {Cp*M(μ-Cl)₃MCp*}₂[{(C₆F ₅)₂M′ (μ-Cl)}₂] (M = Rh, Ir; M′ = Pt, Pd) (5-8) as a result of chloride transfer. The structures of [(PEt₃)(η⁵- C₅Me₅)Rh(μ-Cl)₂Pt(C₆F ₅)₂] (1) and {Cp*Rh(μ-Cl)₃RhCp* }2[{(C₆F₅)₂Pd(μ-Cl)}₂] (6) have been determined by X-ray diffraction analyses. The reactivity of the new chloride-bridged heterobinuclear compounds 1-4 towards the alkynylating agents [M″(C≡CR)]_n (M″ = Cu, Ag) has also been investigated: a new type of tetranuclear product, [(PEt₃)Cp* M(μ-1κC^α:η²-C≡CPh) ₂M″₂(μ-4κC^α:η ²-C≡CPh)₂Pt(C₆F₅) ₂] (M = Rh, Ir; M″ = Cu, Ag) (9-12), was obtained, and fully characterized in the case of complex [(PEt₃)Cp*Rh(μ-1κC^α:η ²-C≡CPh)₂Cu₂(μ-4κC ^α:η²-C≡CPh)₂Pt(C ₆F₅)₂] (9).

Full text of DOI:10.1002/1099-0682(200106)2001:6<1631::AID-EJIC1631>3.0.CO;2-6

FULL PAPER
Synthesis of Novel Heterotetrametallic (d6-d10-d8) Polyalkynyl Complexes
Starting from Heterobimetallic Chloride-Bridged (d6-d8) Compounds
[a]
[b]
[b]
[a]
[b]
´
´
´
Irene Ara, Jesus R. Berenguer, Eduardo Eguizabal, Juan Fornies,* Elena Lalinde,*
[a]
´
and Antonio Martın
´
Dedicated to Prof. R. Uson on the occasion of his 75th birthday
Keywords: Iridium / Rhodium / Heteropolymetallics / Chloro-bridged complexes / Alkynide-bridged complexes
The reaction between the half-sandwich cyclopentadienyl
complexes [M(η5-C5Me5)Cl2(PEt3)] (M = Rh, Ir) and [cis-
MЈ(C6F5)2(thf)2] (MЈ = Pt, Pd; thf = tetrahydrofuran) affords
C5Me5)Rh(µ-Cl)2Pt(C6F5)2] (1) and {Cp*Rh(µ-Cl)3RhCp*
}2[{(C6F5)2Pd(µ-Cl)}2] (6) have been determined by X-ray dif-
fraction analyses. The reactivity of the new chloride-bridged
the corresponding chloride-bridged heterobinuclear Rh,Ir/ heterobinuclear compounds 1−4 towards the alkynylating
Pt,Pd complexes [(PEt3)(η5-C5Me5)M(µ-Cl)2MЈ(C6F5)2] (1−4).
In contrast, similar reactions with the chloro-bridged binuc-
lear compounds [{M(η5-C5Me5)Cl(µ-Cl)}2] (M = Rh, Ir) lead M(µ-1κCα:η2-CϵCPh)2MЈЈ2(µ-4κCα:η2-CϵCPh)2Pt(C6F5)2]
agents [MЈЈ(CϵCR)]n (MЈЈ = Cu, Ag) has also been investig-
ated: new type of tetranuclear product, [(PEt3)Cp*
a
instead to the unexpected mixed salt complexes {Cp*M(µ-
Cl)3MCp*}2[{(C6F5)2MЈ(µ-Cl)}2] (M = Rh, Ir; MЈ = Pt, Pd) (5−8)
as a result of chloride transfer. The structures of [(PEt3)(η5-
(M = Rh, Ir; MЈЈ = Cu, Ag) (9−12), was obtained, and fully
characterized in the case of complex [(PEt3)Cp*Rh(µ-1κCα:η2-
CϵCPh)2Cu2(µ-4κCα:η2-CϵCPh)2Pt(C6F5)2] (9).
Introduction
and hetero-bridged µ-alkynyl,µ-halide [(PEt3)Cp*M(µ-
CϵCR)(µ-X)MЈ(C6F5)2] heterobinuclear Rh,IrIII/Pt,PdII
complexes,[4g] simply by treating mono [MCp*
(CϵCR)X(PEt3)] or bis(alkynyl) [MCp*(CϵCR)2(PEt3)]
compounds with [cis-MЈ(C6F5)2(thf)2]. As a continuation of
our work in this field, and in order to complete this series
with respect to the bridging system, we report herein the
synthesis of the dichloro-bridged heterobinuclear complexes
[(PEt3)Cp*M(µ-Cl)2MЈ(C6F5)2] (M ϭ Rh, MЈ ϭ Pt: 1, Pd:
2; M ϭ Ir, MЈ ϭ Pt: 3, Pd: 4) and the crystal structure of
1. Furthermore, in order to explore the potential utility of
these new compounds, we have attempted the preparation
of alkynyl-bridged complexes by treating them with ethynyl-
ating agents such as [CuCϵCR]x and [Ag(CϵCR)]x. These
reactions led to the synthesis of a new type of heteropolynu-
clear alkynyl-bridged complexes [(PEt3)Cp*M(µ-1κCα:η2-
CϵCPh)2MЈЈ2(µ-4κCα:η2-CϵCPh)2Pt(C6F5)2] (M ϭ Rh,
Ir; MЈЈ ϭ Cu, Ag) (9؊12), in which two widely divergent
bis(alkynyl) metal fragments (d6 and d8) are connected
through d10 (Cu or Ag) metal ions. We also describe similar
reactions between [{MCp*Cl(µ-Cl)}2] (M ϭ Rh, Ir) and
[cis-MЈ(C6F5)2(thf)2] (MЈ ϭ Pt, Pd) that involve chloride-
transfer to yield the mixed salt complexes {Cp*M(µ-
Cl)3MCp*}2[{(C6F5)2MЈ(µ-Cl)}2] (M ϭ Rh, Ir; MЈ ϭ Pt,
Pd) (5؊8), and we present the crystal structure of {Cp*
Rh(µ-Cl)3RhCp*}2[{(C6F5)2Pd(µ-Cl)}2] (6).
The chemistry of bimetallic complexes has aroused much
interest and has led to great development in the field of
organometallic chemistry.[1] In this area, there have been
many reports detailing the preparation and chemistry of
symmetrical or asymmetrical dichloro-bridged homobinuc-
lear complexes,[2][3l] mainly because they play a prominent
role as starting materials in organometallic chemistry and
because of their relevance in catalysis. In marked contrast,
the heterobinuclear analogues Lm(µ-Cl)2MЈLn
very scarce and their chemistry remains essentially undocu-
mented, although efforts to develop this chemistry have re-
cently been reported.[3fϪ3p]
This paucity of heterobinuclear compounds containing
chloride bridging ligands, as well as the potentially rich
chemistry that may be expected in these systems, prompted
us to prepare binuclear compounds containing RhIII or IrIII
fragments together with [cis-MЈ(C6F5)2] (MЈ ϭ Pt, Pd) un-
its. We were interested in using these systems as precursors
for alkynyl-bridged heteropolynuclear complexes.[4] In the
course of our ongoing research on alkynyl complexes, we
have recently succeeded in synthesizing the first homo-
bridged bis(µ-alkynyl) [(PEt3)Cp*M(µ-CϵCR)2MЈ(C6F5)2]
[3aϪ3e]
are
[a]
´
´
Departamento de Quımica Inorganica, Instituto de Ciencia de
´
Materiales de Aragon, Universidad de Zaragoza Ϫ Consejo
´
Superior de Investigaciones Cientıfica,
50009 Zaragoza, Spain
Results and Discussion
Fax: (internat.) ϩ34Ϫ976/761187
E-mail: forniesj@posta.unizar.es
Synthesis of Hetero- and Homobimetallic Chloride-Bridged
Complexes
[b]
´
´
´
Departamento de Quımica Ϫ Grupo de Sıntesis Quımica de La
Rioja, UA-CSIC, Universidad de La Rioja,
26004 Logron˜o, Spain
The preparative results are summarized in Scheme 1. The
reaction of compounds [cis-MЈ(C6F5)2(thf)2] (MЈ ϭ Pt, Pd)
Fax: (internat.) ϩ34Ϫ941/299621
E-mail: elena.lalinde@dq.unirioja.es
Eur. J. Inorg. Chem. 2001, 1631Ϫ1640
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0606Ϫ1631 $ 17.50ϩ.50/0
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I. Ara, J. R. Berenguer, E. Eguizabal, J. Fornies, E. Lalinde, A. Martın
FULL PAPER
Scheme 1
with metallo species bearing potentially bridging groups in deposition of metallic palladium. The complexes have been
cis or even trans positions has proved to be an excellent characterized by analytical and spectroscopic techniques. In
preparative method for the synthesis of bi- and polymetallic addition, the structure of complex 1 has been established
complexes.[4a,4g,5] Therefore, we considered it appropriate to by an X-ray diffraction study. The IR spectra show two
use this strategy for the synthesis of the desired doubly absorptions in the 785Ϫ812 cmϪ1 region attributable to the
chloride-bridged heterobinuclear complexes 1Ϫ4. Treat- x-sensitive mode of the C6F5 groups (AЈ, AЈЈ; Cs), thus in-
ment of a red solution of [MCp*Cl2(PEt3)] (M ϭ Rh, Ir) dicating the presence of a cis-M(C6F5) moiety.[6] Further-
in acetone with 1 equivalent of the solvated platinum or more, all the complexes show bands (247Ϫ277 cmϪ1) asso-
palladium complex [cis-MЈ(C6F5)2(thf)2] immediately gave ciated with the ν(MϪCl) stretching vibrations (2AЈ ϩ 2 AЈЈ;
an orange solution, from which the corresponding com- Cs) of the bridges.
plexes 1؊4 could be isolated as orange solids in high yields
The NMR spectroscopic data are consistent with the
(i, Scheme 1). It should be mentioned that several neutral solid-state structure of complex 1. This complex crystallizes
[(ppy)2M(µ-Cl)2MЈ(PR3)Cl] (M ϭ Rh, Ir; MЈ ϭ Pt, Pd; with a bent RhCl2Pt central core, and the conformer found
ppy ϭ 2-phenylpyridine anion; R ϭ Bu, Et) or cationic (see Figure 1) is that in which the Pt(C6F5)2 unit lies endo
[(chel)M(µ-Cl)2MЈ(PEt3)2](BF4) (M ϭ Rh, Ir; MЈ ϭ Pt, Pd; to the Cp* ligand. The room and low-temperature NMR
chel
ϭ
anion of 2-phenylpyridine, benzo[4]quinoline, spectroscopic data (1H, 31P{1H}, 19F, and 13C{1H}) reveal
C6H5CHRNMe2, or η3-allyl) heterobinuclear (d6-d8) chlor- no evidence of possible conformers (see Experimental Sec-
ide-bridged complexes have been very recently prepared by tion for details), although a possible rapid interconversion
metathesis reactions from the respective chloro-bridged of conformers (fast inversion of the central RhCl2Pt core)
homodimeric compounds.[3l,3o] In addition, related dicat- cannot be excluded. Only the 19F NMR spectra are temper-
ionic [(PMe3)(η5-C5Me5)M(µ-Cl)2PtL2]2ϩ(OTf)Ϫ2 (M ϭ Rh, ature dependent. Thus, in accordance with the structure de-
Ir; L2 ϭ dppp, 2 PPh3) complexes have been prepared by a picted in Scheme 1 (see also Figure 1), the room temper-
similar route starting from the bis(triflate) species [MCp* ature 19F NMR spectra in [D6]acetone show only one type
(PMe3)(OTf)2] (M ϭ Rh, Ir) and the corresponding dichlor- of C6F5 ligand, confirming the equivalence of the two C6F5
oplatinum derivatives.[3g]
moieties. However, they exhibit the typical AAЈMXXЈ pat-
The heterobinuclear platinum complexes 1 and 3 remain tern of three signals of relative intensity 2:1:2, evidencing
stable indefinitely, both in the solid state and in solution, that the two halves of each C6F5 ring appear equivalent at
but the mixed palladium compounds are only stable in the room temperature, and indicating that these complexes are
solid state. In solution, 2 and 4 slowly decompose with the not rigid in solution. As expected, on lowering the temper-
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Eur. J. Inorg. Chem. 2001, 1631Ϫ1640

Synthesis of Novel Heterotetrametallic Polyalkynyl Complexes
FULL PAPER
chloride-bridged
symmetrical
bimetallic
and
species
(NBu4)2[(C6F5)2Pt(µ-Cl)2Pt(C6F5)2][8]
[{Rh(η5-
C5Me5)Cl(µ-Cl)}2].[9] A recent theoretical study seems to
confirm the observation that asymmetric chloro-bridged
complexes tend to have a bent structural arrangement.[3p]
Thus, the cationic mixed derivative [(bzq)2Rh(µ-
Cl)2Pt(PBu3)2]ϩ is also considerably bent (29.4°)[3o] and
similar nonplanar structures, albeit less severely distorted,
have also been found in [(PMe3)Cp*Ir(µ-Cl)2Pt(dppp)]2ϩ
(ca. 11°)[3g] and [(ppy)2Rh(µ-Cl)2PtCl(PBu3)] (13.2°).[3l]
However, other theoretical and structural analyses of
square-planar d8 metal complexes of the type [L2M(µ-
Cl)2ML2] seem to suggest that attractive metalϪmetal inter-
actions are one of the main factors responsible for the ob-
served bending.[10] In complex 1, the PtϪRh distance of
Figure 1. Molecular structure of [(PEt3)(η5-C5Me5)Rh(µ- 3.407(1) A suggests that the observed puckering does not
˚
Cl)2Pt(C6F5)2] (1) showing the atom labelling scheme (ellipsoids are
lead to any significant metalϪmetal bonding interaction.
However, this distance is markedly shorter than those ob-
drawn at a 50% probability level; hydrogen atoms have been omit-
ted for clarity)
served in the respective homobimetallic species
[8]
[{(C6F5)2Pt(µ-Cl)}2]2Ϫ [3.528(1) A]
ature (to Ϫ50 °C), five distinct fluorine resonances become C5Me5)Cl(µ-Cl)}2] [3.719(1) A]
and [{Rh(η5-
˚
[9]
˚
and in the mixed
clearly resolved for all the complexes. We note that a pos- RhIIIϪPtII ortho-metallated derivatives [(ppy)2Rh(µ-
[3l]
˚
sible fast inversion of the central MCl2MЈ core, which can- Cl)2PtCl(PBu3)]
not be excluded, would not exchange the two halves of each Cl)2Pt(PBu3)2]ϩ (3.63 A).
C6F5 moiety. Therefore, the most likely dynamic process above is more akin to that found in the chloride/alkynide
(3.61
A)
and
[(bzq)2Rh(µ-
[3o]
˚
Clearly, the value mentioned
that would account for the exchange of the halves of the hetero-bridged
C6F5 rings is their free rotation about the PtϪCi(C6F5) CϵCPh)Pt(C6F5)2] [3.371(1) A].
compound
[(PEt3)Cp*Rh(µ-Cl)(µ-
[4g]
˚
bonds. From the coalescence temperature Tc (258 K) and
˚
Table 1. Selected bond lengths [A] and angles [deg.] in complex
[(PEt3)Cp*Rh(µ-Cl)2Pt(C6F5)2] (1) (Cp*cent: centroid of the Cp*
group. Symmetry transformations used to generate equivalent
atoms (a): x, Ϫy ϩ 1/2, z)
the difference in chemical shift ∆ν of the Fo signals, a ∆G#
value of 51 kJ·molϪ1 has been calculated for 4.[7] For com-
plex 1, the 19F NMR spectra have also been recorded in
CDCl3 and both the room and low-temperature (Ϫ50 °C)
spectra were found to be almost identical to those obtained
in [D6]acetone solution. This fact suggests that dissociative
processes, such as the dissociation of an MЈ(C6F5)2 unit or
chlorideϪMЈ (MЈ ϭ Pt, Pd) bond breaking, which would
probably be solvent dependent, are unlikely.
RhϪCl(1)
RhϪCp*cent
PtϪCl(1)
2.409(1)
1.799(1)
2.381(1)
RhϪP
PtϪC(1)
Rh···Pt
2.313(2)
1.959(4)
3.407(1)
PϪRhϪCl(1)
PϪRhϪCp*cent
PtϪCl(1)ϪRh
C(1)ϪPtϪCl(1)
89.27(4)
133.04(5)
90.65(3)
92.07(12)
Cl(1)ϪRhϪCl(1a)
Cl(1)ϪRhϪCp*cent
C(1)ϪPtϪC(1a)
84.02(5)
123.48(3)
90.6(2)
A definitive structural assignment of the heterobimetallic
complexes 1؊4 has been established by an X-ray diffraction
study on complex [(PEt3)(η5-C5Me5)Rh(µ-Cl)2Pt(C6F5)2]
(1, Figure 1). Suitable dark-orange crystals were obtained
by slow diffusion of hexane into a solution of 1 in acetone metalϪchlorine distances [RhϪCl(1) 2.409(1) A; PtϪCl(2)
at low temperature (Ϫ30 °C). Selected bond lengths and 2.381(1) A] rather similar to those found in [(PEt3)Cp*
Cl(1)ϪPtϪCl(1a)
85.22(5)
The bridging chloride is slightly asymmetric, with
˚
˚
˚
angles are collected in Table 1. The structure confirms that Rh(µ-Cl)(µ-CϵCPh)Pt(C6F5)2] (ഠ 2.43 A). This structural
the complex contains an Rh(III) centre in a pseudo-octa- feature is in marked contrast to the dichloro bridges in the
hedral environment, formed by the η5-bonded C5Me5 cationic
[(bzq)2Rh(µ-Cl)2Pt(PBu3)2]ϩ
and
neutral
group, which occupies three formal coordination sites, the [(ppy)2Rh(µ-Cl)2PtCl(PBu3)] complexes, which are highly
˚
˚
PEt3, and the two bridging chlorides, and a Pt atom that asymmetric (RhϪCl ഠ 2.53 A; PtϪCl 2.36Ϫ2.40 A). The
completes its usual square-planar coordination with two σ- Cl(1)RhCl(1a) [84.02(5)°] and Cl(1)PtCl(1a) [85.22(5)°]
C6F5 groups. The geometries around both metal centres are angles are almost identical and are slightly smaller than the
unexceptional for fragments of this type and are similar to angle at the chlorine atom [90.65(3)°].
those previously observed in related homo-bridged µ-bis(al-
With the aim of obtaining binuclear derivatives of the
kynyl) and hetero-bridged (µ-Cl)(µ-alkynyl) d6-d8 sys- general formula [(S)Cp*M(µ-Cl)2MЈ(C6F5)2] with one va-
tems.[4g] The central Rh(µ-Cl)2Pt core shows a marked devi- cant site for bonding, where S could be a solvent molecule
ation from planarity, with a dihedral angle between the such as acetone or thf, we also explored the reactivity of
ClRhCl plane and the platinum coordination plane the tetrahydrofuran adducts [cis-MЈ(C6F5)2(thf)2] towards
of 31.5°. This structural feature contrasts with the planar the binuclear derivatives [{MCp*Cl(µ-Cl)}2] in acetone in a
cores previously found in the corresponding doubly 2:1 molar ratio. However, contrary to our expectations,
Eur. J. Inorg. Chem. 2001, 1631Ϫ1640
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I. Ara, J. R. Berenguer, E. Eguizabal, J. Fornies, E. Lalinde, A. Martın
FULL PAPER
these reactions did not afford the desired heterobimetallic
complexes; instead, low yields of the mixed ionic 2:1 salts
[Cp*M(µ-Cl)3MCp*]2[{(C6F5)2MЈ(µ-Cl)}2]
(5؊8)
(ii,
Scheme 1) were obtained. Predictably, better yields were ob-
tained when the reactions were carried out in a 1:1 molar
ratio (see Experimental Section). In these reactions, the
platinum and palladium fragments ‘‘cis-MЈ(C6F5)2’’ act as
abstractors of chloride ligands giving [cis-(C6F5)2MЈCl]Ϫ,
which dimerizes to [(C6F5)2MЈ(µ-Cl)2MЈ(C6F5)2]2Ϫ, thus
leaving the binuclear half-sandwich cationic complexes [Cp*
M(µ-Cl)3MCp*]ϩ with the chloro-bridges. Both cationic
[(Cp*M)2(µ-Cl)3]BF4 (M ϭ Rh, Ir)[11a] species have previ-
ously been generated in a more rational manner by treating
the binuclear neutral derivatives with AgClO4 or TlBF4 in
CH2Cl2 and, in the case of [Cp*Rh(µ-Cl)3RhCp*]ϩ, also by
reaction of [{RhCp*Cl(µ-Cl)}2] with NaBPh4.[11b] We also
note that chloride-transfer reactions between the highly
charged fragments [PtCl6]2Ϫ and [RhCp*(NCMe)3]2ϩ [12]
as
,
well as between the neutral half-sandwich complexes [{(p-
cym)RuCl(µ-Cl)}2] or [{MCp*Cl(µ-Cl)}2] (M ϭ Rh, Ir) and
the cationic chloride-bridged palladium(II) substrate,[3o]
have been reported previously.
The ionic compounds 5؊8, which were obtained as or-
ange (5, 6) or yellow (7, 8) solids, are only slightly soluble
in organic solvents, the solubility being especially low in the
case of the iridium derivatives. These complexes have been
characterized by a combination of microanalysis, mass
spectrometry [ES(ϩ) and ES(Ϫ)], and spectroscopic
methods (IR, 1H and 19F NMR) (see Experimental Sec-
tion). Mass spectra in the ES(ϩ) mode feature the expected
[M2Cp*2Cl3]ϩ (M ϭ Rh, Ir) ion molecular fragment and in
the ES(Ϫ) or APCI(Ϫ) modes they feature the
[MЈ(C6F5)2Cl]Ϫ (MЈ ϭ Pt, Pd) ion fragment arising from a
fragmentation of the binuclear anion.
The molecular structure of 6 was confirmed by single-
crystal X-ray analysis (Figure 2, Table 2). As can be seen,
it comprises two [(Cp*Rh)2(µ-Cl)3]ϩ ions and a binuclear
dianionic [(C6F5)2Pd(µ-Cl)2Pd(C6F5)2]2Ϫ ion. The struc-
tural features of the cationic fragment are identical to those
reported previously[12,13] hence they are not discussed here.
Figure 2. Structure and atom numbering scheme for the anion
[{(C6F5)2Pd(µ-Cl)}2]2Ϫ (a) and one of the cations [Cp*Rh(µ-
Cl)3RhCp*]ϩ (b) in complex 6 (ellipsoids are drawn at a 50% prob-
ability level; hydrogen atoms have been omitted for clarity)
1.31 and 1.28 A, respectively,[15] the Pd···Pd distance should
˚
˚
be ca. 0.06 A longer than that found in the diplatinum an-
[8]
˚
ion [Pt···Pt 3.528(1) A], thus suggesting that the experi-
In contrast, although the crystal structures of the anions
˚
[8]
[(C6F5)2Pt(µ-Cl)2Pt(C6F5)2]2Ϫ
and [(C6F5)2Ni(µ-Cl)2Ni-
mental value found in the dipalladium anion [3.464(2) A]
(C6F5)2]2Ϫ [14] have been published, the structure of the cor-
responding dipalladium species remains unknown. There-
fore, this study completes the series with its final member,
[(C6F5)2Pd(µ-Cl)2Pd(C6F5)2]2Ϫ, providing an opportunity
for quantitative structural comparisons. Selected distances
and angles are compared in Table 3. It is interesting to note
that one of the most remarkable differences can be seen in
the MЈ2Cl2 core. Thus, while the nickel and platinum anions
exhibit typical[3p,10] MЈ2Cl2C4 planar cores (both have a
crystallographic centre of inversion), the anion
[(C6F5)2Pd(µ-Cl)2Pd(C6F5)2]2Ϫ found in 6 displays a slightly
might be reduced due to the small degree of bending.
˚
The PdϪC [2.001(13)Ϫ2.023(12) A] and PdϪCl
˚
[2.404(4)Ϫ2.421(4) A] bridging lengths are comparable with
those seen in [(C6F5)2Pd(µ-Cl)2Pt(PEt3)2] [PdϪC 1.980(7),
˚
˚
1.992(7) A; PdϪCl 2.402(2), 2.449(2) A], which is the only
derivative to be crystallographically characterized that also
contains the ‘‘(C6F5)2PdCl2’’ fragment.[3f]
Synthesis of Tetranuclear [(PEt3)Cp*M(µ-CϵCPh)2MЈЈ2(µ-
CϵCPh)2Pt(C6F5)2] Complexes (9؊12)
We have recently been interested in exploring the reactiv-
bent chloro-bridge, with the dihedral angle defined by the ity of alkynyl platinate(II) complexes towards suitable elec-
corresponding palladium coordination planes being 13°. trophilic metal fragments as a useful route to heteropoly-
˚
The resulting Pd···Pd distance of 3.464(2) A is, as expected, nuclear
complexes
containing
alkynyl
bridging
longer than that found in the nickel derivative [Ni···Ni 3.28 ligands.[4a,4b,4dϪ4g,4iϪ4k] As an alternative route, we decided
[14]
˚
A].
However, assuming covalent radii for Pd and Pt of to examine the potential utility of the new chloride-bridged
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Synthesis of Novel Heterotetrametallic Polyalkynyl Complexes
FULL PAPER
˚
produces, after standard work-up, moderate (61Ϫ75%) or
low yields (RhAg2Pt 10, 27%) of yellow products that can
be formulated as tetrametallic compounds [(PEt3)Cp*M(µ-
1κCα:η2-CϵCPh)2MЈЈ2(µ-4κCα:η2-CϵCPh)2Pt(C6F5)2]
(M ϭ Rh, Ir; MЈЈ ϭ Cu, Ag) (9؊12). Unfortunately, start-
ing from the mixed palladium complexes 2 and 4, consider-
able decomposition takes place and the analogous reactions
with the tert-butyl alkynyl substrates [MЈЈCϵCtBu]x (M ϭ
Cu, Ag) yield only complicated mixtures of products, which
we have not been able to separate. We also note that the
reactions of 1 and 3 with a smaller excess of the polymeric
alkynides (2 equivalents) produced mixtures of compounds
in which the final tetranuclear species and the heterobinu-
clear [(PEt3)Cp*M(µ-CϵCPh)(µ-Cl)Pt(C6F5)2] were easily
detectable by 31P{1H} NMR spectroscopy.
The new tetranuclear compounds 9؊12 have been fully
characterized by analytical and spectroscopic means and
the molecular structure of 9 has been unambiguously con-
firmed by X-ray diffraction analysis. The presence of
bridging alkynyl ligands is evident from the IR spectra,
which show two ν(CϵC) absorptions in the expected region
(1969Ϫ2070 cmϪ1).[4,16] These bands appear at lower fre-
quencies in the copper derivatives [2009 (s br), 1969 (sh)
cmϪ1 9; 2006 (s), 1969 (s) cmϪ1 11] than in their silver coun-
terparts [2059 (s br) cmϪ1 10; 2070 (m), 2036 (m) cmϪ1 12]
suggesting, in line with previous observations,[16Ϫ18] that the
η2-alkyne metal interaction is stronger in copper than in
silver complexes. Their NMR spectra (1H, 31P) confirm the
presence of different groups (Cp*, PEt3, CϵCPh) and, in
particular, the room temperature 19F NMR spectra reveal
effective mirror planes that render the two C6F5 ligands
equivalent. Simple AAЈMXXЈ (2 Fo, Fp, 2 Fm) patterns are
seen for all the complexes, presumably because the free ro-
tation of the C6F5 rings is relatively fast at room temper-
ature. However, low-temperature spectra could not be ob-
tained due to the low solubilities of the complexes. Further-
more, their relatively low stabilities in solution at room tem-
perature also precluded characterization by 13C{1H} NMR
spectroscopy. Yellow crystals of [(PEt3)Cp*Rh(µ-
CϵCPh)2Cu2(µ-CϵCPh)2Pt(C6F5)2] 9 suitable for an X-ray
diffraction study were isolated by slow diffusion of hexane
into a CH2Cl2 solution at low temperature (Ϫ30 °C). Fig-
Table 2. Selected bond lengths (A) and angles (deg.) in complex
{Cp*Rh(µ-Cl)3RhCp*}2[{(C6F5)2Pd(µ-Cl)}2] (6) (C*1, C*2, C*3,
C*4: centroids of the Cp* groups)
Pd(1)ϪC(1)
Pd(1)ϪCl(1)
Pd(2)ϪC(13)
Pd(2)ϪCl(1)
Pd(1)··Pd(2)
Rh(1)ϪCl(3)
Rh(1)ϪCl(5)
Rh(2)ϪCl(3)
Rh(2)ϪCl(5)
Rh(3)ϪC*3
Rh(3)ϪCl(7)
Rh(4)ϪC*4
Rh(4)ϪCl(7)
Rh(3)··Rh(4)
2.023(12)
2.421(4)
2.008(13)
2.411(3)
3.464(2)
2.473(4)
2.473(3)
2.479(4)
2.476(4)
1.773(1)
2.452(4)
1.766(1)
2.472(4)
3.246(2)
Pd(1)ϪC(7)
Pd(1)ϪCl(2)
Pd(2)ϪC(19)
Pd(2)ϪCl(2)
Rh(1)ϪC*1
Rh(1)ϪCl(4)
Rh(2)ϪC*2
Rh(2)ϪCl(4)
Rh(1)··Rh(2)
Rh(3)ϪCl(6)
Rh(3)ϪCl(8)
Rh(4)ϪCl(6)
Rh(4)ϪCl(8)
2.014(12)
2.413(3)
2.001(13)
2.404(4)
1.749(1)
2.469(4)
1.769(1)
2.472(3)
3.246(2)
2.467(4)
2.443(4)
2.480(4)
2.457(4)
Cl(1)ϪPd(1)ϪCl(2)
Cl(2)ϪPd(1)ϪC(1)
Cl(1)ϪPd(2)ϪCl(2)
Cl(2)ϪPd(2)ϪC(13)
Pd(1)ϪCl(1)ϪPd(2)
Cl(3)ϪRh(1)ϪCl(4)
Cl(4)ϪRh(1)ϪCl(5)
C*1ϪRh(1)ϪCl(4)
Cl(3)ϪRh(2)ϪCl(4)
Cl(4)ϪRh(2)ϪCl(5)
C*2ϪRh(2)ϪCl(4)
Cl(6)ϪRh(3)ϪCl(7)
Cl(7)ϪRh(3)ϪCl(8)
C*3ϪRh(3)ϪCl(7)
Cl(6)ϪRh(4)ϪCl(7)
Cl(7)ϪRh(4)ϪCl(8)
C*4ϪRh(4)ϪCl(7)
Rh(1)ϪCl(3)ϪRh(2)
Rh(1)ϪCl(5)ϪRh(2)
Rh(3)ϪCl(7)ϪRh(4)
87.23(12)
90.0(4)
87.66(12)
91.0(4)
91.60(11)
81.49(13)
81.49(12)
130.90(10)
81.31(12)
81.39(11)
132.05(11)
81.7(2)
Cl(1)ϪPd(1)ϪC(7)
C(1)ϪPd(1)ϪC(7)
Cl(1)ϪPd(2)ϪC(19)
C(13)ϪPd(2)ϪC(19)
Pd(1)ϪCl(2)ϪPd(2)
Cl(3)ϪRh(1)ϪCl(5)
C*1ϪRh(1)ϪCl(3) 130.07(13)
C*1ϪRh(1)ϪCl(5) 131.91(12)
Cl(3)ϪRh(2)ϪCl(5)
C*2ϪRh(2)ϪCl(3) 130.07(12)
C*2ϪRh(2)ϪCl(5) 130.47(11)
Cl(6)ϪRh(3)ϪCl(8)
C*3ϪRh(3)ϪCl(6) 130.39(13)
C*3ϪRh(3)ϪCl(8) 131.09(14)
Cl(6)ϪRh(4)ϪCl(8)
91.0(4)
91.9(5)
91.0(4)
90.4(5)
91.95(11)
82.06(12)
81.89(13)
81.5(2)
82.2(2)
131.17(11)
81.0(2)
81.0(2)
81.5(2)
C*4ϪRh(4)ϪCl(6) 131.59(13)
C*4ϪRh(4)ϪCl(8) 130.62(15)
Rh(1)ϪCl(4)ϪRh(2) 82.16(10)
Rh(3)ϪCl(6)ϪRh(4) 81.72(12)
Rh(3)ϪCl(8)ϪRh(4) 82.67(12)
131.71(12)
81.94(10)
81.99(10)
82.18(13)
˚
Table 3. Comparison of selected bond lengths [A] and angles [deg.]
in the anions [(C6F5)2MЈ(µ-Cl)2MЈ(C6F5)2]2Ϫ
Parameter
MЈ ϭ Ni
MЈ ϭ Pd
MЈ ϭ Pt
MЈϪCaverage
MЈϪClaverage
ClϪMЈϪCl
MЈϪClϪMЈ
MЈ····MЈ
1.880(3)
2.253(1)
86.71(3)
93.29(3)
3.28
2.012(13)
2.412(4)
87.45(12)average
91.78(11)average
3.464(2)
1.984(10)
2.391(3)
84.9(1)
95.1(1)
3.528(1)
heterobinuclear compounds 1؊4 as precursors to alkynyl- ure 3 depicts its molecular structure, while selected bond
bridged species by exploring their reactivity towards the lengths and angles are summarized in Table 4.
well-known ethynylating agents [MЈЈ(CϵCR)]x (MЈЈ ϭ Cu,
The most remarkable aspect of the structure is that two
Ag; R ϭ Ph, tBu). The reactions of the polymeric acetylides very different bis(alkynyl) metal fragments ‘‘RhCp*
[Cu(CϵCR)]x and [Ag(CϵCR)]x with transition metal hal- (CϵCPh)2(PEt3)’’ and ‘‘cis-Pt(C6F5)2(CϵCPh)2’’ are con-
ide complexes [MLnXm] have been extensively investigated. nected through two copper centres. As for complex 1, of
Simple substitution processes giving the corresponding the two possible conformers of complex 9, only that in
mononuclear complexes [MLn(CϵCR)m], as well as the which the platinum unit lies endo to the Cp* ring is ob-
formation of polynuclear species generated by further inter- served (Figure 3, b). As expected, the Rh centre is tetrahed-
action of the latter with MX species (X ϭ halide or rally coordinated, being surrounded by the centroid of the
CϵCR), have been reported.[4g,16]
Cp* ring, the PEt3, and two σ-carbon atoms of the alkynyl
The results of the reactions of 1؊4 with [MЈЈ(CϵCR)]x groups, which act as bridging ligands between the two cop-
(MЈЈ ϭ Cu, Ag; R ϭ Ph, tBu) are shown in Scheme 1 (iii). per atoms. The Pt atom is located in a slightly distorted
As can be seen, only the treatment of the platinum mixed square-planar coordination environment made up of four
species [(PEt3)Cp*M(µ-Cl)Pt(C6F5)2] (1, 3) with the pheny- σ-carbon atoms, two from the mutually cis C6F5 rings and
lethynyl substrates (10 equiv. for 9 and 4.5 equiv. for 10؊12) two from the CϵCPh ligands, the latter also being η2-bon-
Eur. J. Inorg. Chem. 2001, 1631Ϫ1640
1635

´
´
´
I. Ara, J. R. Berenguer, E. Eguizabal, J. Fornies, E. Lalinde, A. Martın
FULL PAPER
˚
Table 4. Selected bond lengths (A) and angles (deg.) in complex
[(PEt3)Cp*Rh(µ-1κCα:η2-CϵCPh)2Cu2(µ-4κCα:η2-
CϵCPh)2Pt(C6F5)2] (9) (Cp*cent: centroid of the Cp* group)
PtϪC(21)
PtϪC(1)
PtϪCu(1)
RhϪC(37)
RhϪP
Cu(1)ϪC(30)
Cu(1)ϪC(22)
Cu(2)ϪC(13)
Cu(2)ϪC(38)
C(13)ϪC(14)
C(29)ϪC(30)
RhϪCp*cent
RhϪCu(1)
2.001(8)
2.065(7)
2.9226(14)
2.006(8)
2.289(2)
2.080(7)
2.194(7)
1.984(8)
2.101(8)
1.222(10)
1.213(10)
1.871
PtϪC(13)
PtϪC(7)
PtϪCu(2)
2.014(8)
2.066(7)
2.9384(13)
2.027(8)
2.020(7)
2.098(7)
2.841(2)
1.989(7)
2.230(8)
1.233(10)
1.226(10)
5.247
RhϪC(29)
Cu(1)ϪC(21)
Cu(1)ϪC(29)
Cu(1)ϪCu(2)
Cu(2)ϪC(37)
Cu(2)ϪC(14)
C(21)ϪC(22)
C(37)ϪC(38)
RhϪPt
3.528
RhϪCu(2)
3.217
C(21)ϪPtϪC(13)
C(13)ϪPtϪC(1)
Cu(1)ϪPtϪCu(2)
C(37)ϪRhϪP
92.1(3)
88.2(3)
57.99(3)
87.0(2)
C(1)ϪPtϪC(7)
C(21)ϪPtϪC(7)
C(37)ϪRhϪC(29)
C(29)ϪRhϪP
87.8(3)
91.7(3)
99.3(3)
83.7(2)
C(14)ϪC(13)ϪPt
175.3(7) C(13)ϪC(14)ϪC(15Ј) 161.7(13)
C(13)ϪC(14)ϪC(15) 176(3)
C(21)ϪC(22)ϪC(23) 163.4(8)
C(29)ϪC(30)ϪC(31) 165.2(8)
C(22)ϪC(21)ϪPt
C(30)ϪC(29)ϪRh
C(38)ϪC(37)ϪRh
171.4(7)
167.7(7)
173.8(7)
122.81
C(37)ϪC(38)ϪC(39) 165.7(8) Cp*centϪRhϪC(29)
Cp*centϪRhϪC(37)
Cu(1)ϪRhϪCu(2)
122.23
49.56
Cp*centϪRhϪP
131.03
˚
˚
[1.984(8)Ϫ2.098(7) A] and CuϪCβ [2.080(7)Ϫ2.230(8) A]
distances are, as expected, shorter than the corresponding
AgϪC distances in [Pt2Ag2(C6F5)4(CϵCPh)4]2Ϫ [16j]
but are
,
comparable to those found in related systems such as
˚
[Pt2Cu4(CϵCPh)8]3 [CuϪCα
ϭ
1.981(8)Ϫ2.019(8) A;
[19]
˚
CuϪCβ
ϭ
2.141(9)Ϫ2.161(9)
A],
[Ir2-
˚
Cu4(CϵCPh)8(PPh3)2] [CuϪCα ϭ 1.981(8)Ϫ2.019(8) A;
[16a,16b]
˚
CuϪCβ
ϭ
2.141(9)Ϫ2.161(9) A],
[Mn2Cu(µ-
[20]
CϵCtBu)2(CO)6(dppe)2]ϩ [CuϪCaverage ϭ 2.081(10) A],
˚
and [{Re(CO)5ϪCϵCϪRe(CO)5}2Cu]ϩ [CuϪCaverage
2.055(10) A].
ϭ
Figure 3. (a) View of the molecular structure of [(PEt3)Cp*Rh(µ-
1κCα:η2-CϵCPh)2Cu2(µ-4κCα:η2-CϵCPh)2Pt(C6F5)2] (9) (ellips-
oids are drawn at a 50% probability level; hydrogen atoms have
been omitted for clarity; (b) schematic view of the central core of 9)
[17]
˚
The parameters for the acetylenic frag-
ments (CϪC distances, angles at Cα and Cβ) lie within the
normal ranges for alkynyl σ,π bonding modes.[4,16Ϫ20]
˚
The Cu(1)···Cu(2) distance [2.841(2) A] is slightly shorter
ded to the copper centres. The structural parameters for this
than those found in the cluster [Pt2Cu4(CϵCPh)8]3
˚
fragment [PtϪCα 2.014(8), 2.001(8) A; CαϪPtϪCαЈ
[19]
˚
˚
[3.031(2) A, 3.301(2) A]
and is comparable with those
92.1(3)°] are rather similar to those previously observed for
the tetranuclear anion [Pt2Ag2(C6F5)4(CϵCPh)4]2Ϫ, in
which two identical [cis-Pt(C6F5)2(CϵCPh)2]2Ϫ units are
connected via two silver centres through η2-alkyneϪsilver
interactions.[16j]
The most remarkable feature of the rhodium fragment is
that the CαϪRhϪCαЈ angle (99.3°) is substantially larger
compared to related bite angles in doubly alkynyl-bridged
complexes [(PEt3)Cp*Ir(µ-CϵCR)2MЈ(C6F5)2] [MЈ ϭ Pt,
R ϭ Ph 79.9(8)°; R ϭ SiMe3 76.9(6)°; MЈ ϭ Pd, R ϭ Ph
81.0(7)°], in which the 3-irida-1,4-diyne fragments
[Ir](CϵCR)2 act as chelating bidentate ligands.[4g] This
structural feature may be tentatively attributed to the bi-
dentate bridging nature of the [Rh](CϵCPh)2 unit.
All the alkynyl ligands are η2-bonded to Cu atoms in
such a way that each Cu is stabilized by two alkyne entities
observed in the cluster [Ir2Cu4(CϵCPh)8(PPh3)2] [2.665(6)
[16a,16b]
˚
˚
A, 2.823(5) A]
and in other more common alkynyl
polynuclear copper(I) complexes.[21] Nevertheless, it still
slightly exceeds the van der Waals limit (2.80 A), exclud-
[15]
˚
ing any significant bonding interaction. The Rh···Cu sep-
˚
arations of 3.217 and 3.528 A are considerably longer than
˚
the Pt···Cu distances of 2.9226(14) and 2.9384(13) A, re-
spectively. These latter values are comparable to those seen
[19]
˚
in [Pt2Cu4(CϵCPh)8]3 [2.9187(12)Ϫ3.0272(10) A]
and
are considerably shorter than the sum of the van der Waals
[15]
˚
radii (3.15 A), probably suggesting the presence of some
weak Pt···Cu bonding interactions.[22]
Experimental Section
General Remarks: All reactions were carried out under nitrogen
(one associated with each metal fragment). The CuϪCα atmosphere. Solvents (hexane, alkane mixtures) were dried by
1636 Eur. J. Inorg. Chem. 2001, 1631Ϫ1640

Synthesis of Novel Heterotetrametallic Polyalkynyl Complexes
standard procedures and distilled under dry N2 before use; acetone
FULL PAPER
1
1
δ ϭ 29.66 (d, JRhϪP ϭ 139); at Ϫ50 °C: δ ϭ 30.75 (d, JRhϪP
ϭ
was treated with KMnO4 and distilled under dry N2 prior to use. 138.8). Ϫ FAB(ϩ) MS: m/z (%) ϭ 832 (6) [Mϩ Ϫ Cl Ϫ 1], 700 (21)
[MCp*Cl2(PEt3)],[4g] [MCp*Cl2]2 (M ϭ Rh, Ir),[23] [MCϵCPh]x [Mϩ Ϫ C6F5], 391 (100) [RhCp*Cl(PEt3)ϩ].
(M ϭ Ag,[24] Cu[25]), and [cis-MЈ(C6F5)2(thf)2] (MЈ ϭ Pt, Pd)[26]
3: (0.45 g, 85%). Ϫ C28H30Cl2F10IrPPt (1045.73): calcd. C 32.16, H
were prepared by published methods. Ϫ 1H, 13C, 19F, and 31P NMR
spectra were recorded on a Bruker ARX-300 spectrometer. Chem-
ical shifts are reported in ppm relative to external standards
(SiMe4, CFCl3, and 88% H3PO4) and coupling constants are given
in Hz. Ϫ Infrared spectra were recorded on a PerkinϪElmer 883
spectrometer with samples as Nujol mulls between polyethylene
sheets. Ϫ C, H, N analyses were carried out with PerkinϪElmer
2400 CHNS/O or Carlo Erba EA1110 CHNS-O microanalyzers. Ϫ
2.89; found C 31.94, H 2.89. Ϫ IR: ν˜ ϭ 812 (vs), 800 (vs) cmϪ1
(C6F5)xϪsens; 285 (s), 276 (s), 253 (s) cmϪ1 (MϪCl). Ϫ 1H NMR
([D6]acetone): at 20 °C: δ ϭ 1.14 (m, 9 H, CH3, PEt3), 1.81 (d,
4JPϪH ϭ 1.6, 15 H, Cp*), 2.44 (m, 6 H, CH2, PEt3); at Ϫ50 °C:
4
δ ϭ 1.05 (m, 9 H, CH3, PEt3), 1.81 (d, JPϪH ϭ 2.7, 15 H, Cp*),
2.37 (m, 6 H, CH2, PEt3). Ϫ 13C NMR ([D6]acetone): at Ϫ50 °C:
2
δ ϭ 5.4 (d, JPϪC ϭ 3.3, CH3, PEt3), 7.4 [s, C5(CH3)5], 13.5 (d,
1JPϪC ϭ 35.1, CH2, PEt3), 93.4 (d, JPϪC ϭ 2.3, C5Me5), 134.25
2
Mass spectra were obtained on VG Autospec double-focusing
1
1
(dm, JFϪC ϭ 260, Cm, C6F5), 135.1 (dm, JFϪC ϭ 240, Cp, C6F5),
(FAB) or HP-5989B (APCI and ES) mass spectrometers. Ϫ Con-
ductivities were measured in ca. 5·10Ϫ4  acetone solutions using
a Philips 950/01 conductimeter.
147.2 (dm, JFϪC ϭ 238, Co, C6F5). Ϫ 19F NMR ([D6]acetone): at
1
4
20 °C: δ ϭ Ϫ166.74 (m, JPtϪF ϭ 124.5, 4 Fm), Ϫ164.81 (t, 2 Fp),
Ϫ118.41 (d, JPtϪF ϭ 526.2, 4 Fo); at Ϫ50 °C: δ ϭ Ϫ165.99 (m, 4
3
3
Fm), Ϫ163.86 (t, 2 Fp), Ϫ118.49 (d, JPtϪF ഠ 400, 2 Fo), Ϫ117.98
Synthesis of [(PEt3)Cp*M(µ-Cl)2MЈ(C6F5)2] (M ؍ Rh, MЈ ؍ Pt 1,
MЈ ؍ Pd 2; M ؍ Ir, MЈ ؍ Pt 3, MЈ ؍ Pd 4): A red solution of
[RhCp*Cl2(PEt3)] (0.10 g, 0.23 mmol) in acetone (10 mL) was
treated with [cis-Pt(C6F5)2(thf)2] (0.15 g, 0.23 mmol), which imme-
diately afforded an orange solution. The mixture was stirred for 5
min and then concentrated to dryness. Treatment of the solid res-
idue with cold EtOH (ca. 5 mL) furnished complex 1 as an orange
solid. Complexes 2؊4 (also orange solids) were similarly prepared
but with omission of the stirring for 5 min in the case of the
palladium complexes 2 and 4. Reagents and quantities used: [cis-
Pd(C6F5)2(thf)2] (0.14 g, 0.23 mmol) and [RhCp*Cl2(PEt3)] (0.10 g,
0.23 mmol) for 2; [cis-Pt(C6F5)2(thf)2] (0.34 g, 0.51 mmol) and
[IrCp*Cl2(PEt3)] (0.26 g, 0.51 mmol) for 3; [cis-Pd(C6F5)2(thf)2]
(0.11 g, 0.19 mmol) and [IrCp*Cl2(PEt3)] (0.10 g, 0.19 mmol) for 4.
(d, 3JPtϪF ϭ 509.9, 2 Fo). Ϫ 31P NMR ([D6]acetone): at 20 °C: δ ϭ
4.57 (s); at Ϫ50 °C: δ ϭ 5.80 (s). Ϫ FAB(ϩ) MS: m/z (%) ϭ 1044
(17) [Mϩ Ϫ 2], 878 (6) [Mϩ Ϫ C6F5], 481 (100) [IrCp*Cl(PEt3)ϩ].
4: (0.13 g, 71%) (analyses for a sample recrystallized from CHCl3/
1
1
hexane, which retained a /2 molecule of CHCl3 as observed by H
NMR in [D6]acetone). Ϫ C28H30Cl2F10IrPPd·0.5CHCl3 requires C
33.67, H 3.02; found C 33.99, H 2.74. Ϫ IR: ν˜ ϭ 798 (s), 785 (s)
cmϪ1 (C6F5)xϪsens; 285, 280 (s), 268 (m), 247 (sh) cmϪ1 (MϪCl). Ϫ
1H NMR ([D6]acetone): at 20 °C: δ ϭ 1.16 (m, 9 H, CH3, PEt3),
4
1.81 (d, JPϪH ϭ 1.3, 15 H, Cp*), 2.43 (m, 6 H, CH2, PEt3); at
Ϫ50 °C: δ ϭ 1.14 (m, 9 H, CH3, PEt3), 1.81 (s, 15 H, Cp*), 2.43
(m, 6 H, CH2, PEt3). Ϫ 13C NMR ([D6]acetone): at Ϫ50 °C: δ ϭ
2
7.1 (d, JPϪC ϭ 3.5, CH3, PEt3), 9.05 [s, C5(CH3)5], 13.5 (d,
1JPϪC ϭ 35, CH2, PEt3), 94.5 (d, JPϪC ϭ 2.5, C5Me5), 135.9 (dm,
2
1: (0.20 g, 90%). Ϫ C28H30Cl2F10PPtRh (956.42): calcd. C 35.16,
H 3.16; found C 34.97, H 2.87. Ϫ IR: ν˜ ϭ 812 (vs), 800 (vs) cmϪ1
1JFϪC ϭ 244, Cm, C6F5), 137.3 (dm, 1JFϪC ϭ 241, Cp, C6F5), 147.5
(dm, 1JFϪC ϭ 228, Co, C6F5). Ϫ 19F NMR ([D6]acetone): at 20 °C:
δ ϭ Ϫ165.50 (m, 4 Fm), Ϫ162.95 (t, 2 Fp), Ϫ114.87 (d, 4 Fo); at
Ϫ50 °C: δ ϭ Ϫ164.82 (m, 4 Fm), Ϫ162.11 (t, 2 Fp), Ϫ114.89 (d, 2
Fo), Ϫ114.48 (d, 2 Fo). Ϫ 31P NMR ([D6]acetone): at 20 °C: δ ϭ
2.13 (s); at Ϫ50 °C: δ ϭ 3.07 (s). Ϫ FAB(Ϫ) MS: m/z (%) ϭ 917
(3) [MϪ Ϫ Cl Ϫ 4], 477 (100) [Pd(C6F5)2ClϪ].
1
(C6F5)x-sens; 277 (m), 255 (m), 246 (m) cmϪ1 (MϪCl). Ϫ H NMR
4
(CDCl3): at 20 °C: δ ϭ 1.15 (m, 9 H, CH3, PEt3), 1.74 (d, JPϪH ϭ
2.6, 15 H, Cp*), 2.23 (m, 6 H, CH2, PEt3); at Ϫ50 °C: δ ϭ 1.07 (m,
4
9 H, CH3, PEt3), 1.75 (d, JPϪH ϭ 2.7, 15 H, Cp*), 2.20 (m, 6 H,
CH2, PEt3). Ϫ 13C NMR ([D6]acetone): at 20 °C: δ ϭ 7.3 (d,
1
2JPϪC ϭ 3.4, CH3, PEt3), 9.3 [s, C5(CH3)5], 15.4 (d, JPϪC ϭ 27.8,
1
CH2, PEt3), 101.9 (dd, JRhϪC ϭ 7.1, 2JPϪC ϭ 2.0, C5Me5), 135.95
Synthesis of [Cp*Rh(µ-Cl3)RhCp*]2[(C6F5)2Pt(µ-Cl2)Pt(C6F5)2] (5):
To a red solution of [RhCp*Cl2]2 (0.10 g, 0.162 mmol) in acetone
(20 mL) was added [cis-Pt(C6F5)2(thf)2] (0.11 g, 0.162 mmol)
(molar ratio 1:1) and the mixture was stirred for 30 min. Evapora-
tion of the solvent from the orange suspension and treatment of
the solid residue with Et2O (ca. 5 mL) yielded complex 5 (0.13 g,
68%) as an orange solid. Ϫ C64H60Cl8F20Pt2Rh4 (2294.60): calcd.
C 33.50, H 2.63; found C 33.45, H 2.65. Ϫ Λm (acetone) ϭ 184
1
1
(dm, JFϪC ϭ 253, Cm, C6F5), 136.5 (dm, JFϪC ϭ 241, Cp, C6F5),
148.95 (dm, JFϪC ϭ 231, Co, C6F5). Ϫ 19F NMR (CDCl3): at
1
20 °C: δ ϭ Ϫ163.03 (m, 4 Fm), Ϫ163.99 (t, 2 Fp), Ϫ119.62 (d,
3JPtϪF ϭ 527.7, 4 Fo); at Ϫ50 °C: δ ϭ Ϫ165.34 (m, 2 Fm), Ϫ164.99
3
(m, 2 Fm), Ϫ163.18 (t, 2 Fp), Ϫ119.74 (d, JPtϪF ഠ 525, 2 Fo),
3
Ϫ119.29 (d, JPtϪF ഠ 510, 2 Fo). Ϫ 31P NMR (CDCl3): at 20 °C:
1
δ ϭ 30.27 (d, 1JRhϪP ϭ 138.3); at Ϫ50 °C: δ ϭ 31.31 (d, JRhϪP
ϭ
137.9). Ϫ FAB(ϩ) MS: m/z (%) ϭ 955 (5) [Mϩ Ϫ 1], 789 (10) [Mϩ
ohmϪ1·cm2·molϪ1. Ϫ IR: ν˜ ϭ 811 (vs), 799 (vs) cmϪ1 (C6F5)xϪsens
;
Ϫ C6F5], 391 (100) [RhCp*Cl(PEt3)ϩ].
289 (m), 261 (m), 255 (s), 250 (s) cmϪ1 (MϪCl). Ϫ 1H NMR ([D6]a-
cetone): at 20 °C: δ ϭ 1.77 (s, Cp*). Ϫ 19F NMR ([D6]acetone): at
20 °C: δ ϭ Ϫ167.87 (m, 8 Fm), Ϫ166.87 (t, 4 Fp), Ϫ117.51 (dd,
3JPtϪF ϭ 526.7, 8 Fo). Ϫ APCI(ϩ) MS: m/z (%) ϭ 581 (16)
2: (0.16 g, 78%). Ϫ C28H30Cl2F10PPdRh (867.75): calcd. C 38.76,
H 3.48; found C 38.43, H 3.41. Ϫ IR: ν˜ ϭ 798 (s), 785 (s) cmϪ1
(C6F5)xϪsens; 268 (m, br) (MϪCl). Ϫ 1H NMR ([D6]acetone): at
[Rh2Cp*2Cl3ϩ].
[Pt(C6F5)2ClϪ].
Ϫ APCI(Ϫ) MS: m/z (%) ϭ 565 (100)
4
20 °C: δ ϭ 1.17 (m, 9 H, CH3, PEt3), 1.81 (d, JPϪH ϭ 3, 15 H,
Cp*), 2.38 (m, 6 H, CH2, PEt3); at Ϫ50 °C: δ ϭ 1.07 (m, 9 H, CH3,
4
PEt3), 1.81 (d, JPϪH ϭ 2.7, 15 H, Cp*), 2.32 (m, 6 H, CH2, PEt3).
Complex 5 could also be obtained, albeit in lower yield (0.09 g,
42% based on Rh), by carrying out the reaction starting from
[RhCp*Cl2]2 (0.11 g, 0.18 mmol) and [cis-Pt(C6F5)2(thf)2] (0.24 g,
0.36 mmol) (molar ratio 1:2) and following the same procedure as
above.
2
Ϫ
13C NMR ([D6]acetone): at Ϫ50 °C: δ ϭ 6.1 (d, JPϪC ϭ 3.5,
1
CH3, PEt3), 8.0 [s, C5(CH3)5], 14.4 (d, JPϪC ϭ 27.8, CH2, PEt3),
100.7 (dd, 1JRhϪC ϭ 7.1, 2JPϪC ϭ 2.3, C5Me5), 134.4 (dm, 1JFϪC ϭ
1
2
257, Cm, C6F5), 135.75 (dt, JFϪC ϭ 241, JFϪC ഠ 14, Cp, C6F5),
146.2 (dm, JFϪC ϭ 226, Co, C6F5). Ϫ 19F NMR ([D6]acetone): at
1
20 °C: δ ϭ Ϫ165.63 (m, 4 Fm), Ϫ163.27 (t, 2 Fp), Ϫ114.54 (d, 4
Synthesis of [Cp*Rh(µ-Cl3)RhCp*]2[(C6F5)2Pd(µ-Cl2)Pd(C6F5)2]
Fo); at Ϫ50 °C: δ ϭ Ϫ164.89 (m, 4 Fm), Ϫ162.31 (t, 2 Fp), Ϫ114.47 (6): [cis-Pd(C6F5)2(thf)2] (0.10 g, 0.16 mmol) was added to a red
(d, 2 Fo), Ϫ114.21 (d, 2 Fo). Ϫ 31P NMR ([D6]acetone): at 20 °C:
solution of [RhCp*Cl2]2 (0.10 g, 0.16 mmol) in CH2Cl2 (20 mL)
1637
Eur. J. Inorg. Chem. 2001, 1631Ϫ1640

´
´
´
I. Ara, J. R. Berenguer, E. Eguizabal, J. Fornies, E. Lalinde, A. Martın
FULL PAPER
(molar ratio 1:1) and the mixture was stirred for 30 min. The re-
sulting solution was then concentrated to a small volume (ca.
5 mL), whereupon 6 (0.14 g, 80%) was precipitated as an orange
solid. Ϫ C64H60Cl8F20Pd2Rh4 (2117.26): calcd. C 36.31, H 2.86;
found C 36.16, H 2.58. Ϫ Λm (acetone) ϭ 167 ohmϪ1·cm2·molϪ1
Ϫ IR: ν˜ ϭ 796 (s), 783 (s) cmϪ1 (C6F5)xϪsens; 288 (m), 278 (m), 249
(s) cmϪ1 (MϪCl). Ϫ 1H NMR ([D6]acetone): at 20 °C: δ ϭ 1.77 (s,
Cp*). Ϫ 19F NMR ([D6]acetone): at 20 °C: δ ϭ 166.77 (m, 8 Fm),
Ϫ165.24 (t, 4 Fp), Ϫ113.29 (d, 8 Fo). Ϫ APCI(ϩ) MS: m/z (%) ϭ
581 (100) [Rh2Cp*2Cl3ϩ]. Ϫ APCI(Ϫ) MS: m/z (%) ϭ 477 (16)
[Pd(C6F5)2ClϪ].
Cl)2Pt(C6F5)2] (3) (0.16 g, 0.15 mmol) and [CuCϵCPh]x (0.11 g,
0.69 mmol) for 11; 3 (0.20 g, 0.19 mmol) and [AgCϵCPh]x (0.17 g,
0.81 mmol) for 12.
9: (0.17 g, 75%). Ϫ C60H50Cu2F10PPtRh (1417.13): calcd. C 50.86,
.
H 3.56; found C 50.44, H 3.38. Ϫ IR: ν˜ ϭ 2009 (s br), 1969 (sh)
cmϪ1 (CϵC); 797 (s), 778 (s) cmϪ1 (C6F5)xϪsens. Ϫ 1H NMR
(CDCl3): at 20 °C: δ ϭ 0.91 (m, 9 H, CH3, PEt3), 1.89 (m, 6 H,
4
CH2, PEt3), 2.00 (d, JPϪH ϭ 1.7, 15 H, Cp*), 7.16 (m, 20 H, Ph).
Ϫ
19F NMR (CDCl3): at 20 °C: δ ϭ Ϫ166.06 (m, 4 Fm), Ϫ164.85
(t, 2 Fp), Ϫ116.10 (dd, 3JPtϪF ϭ 376.1, 4 Fo). Ϫ 31P NMR (CDCl3):
at 20 °C: δ ϭ 35.88 (d, 1JRhϪP ϭ 115.7). Ϫ FAB(ϩ) MS: m/z (%) ϭ
1417 (8) [Mϩ ϩ 1], 1148 (20) [Mϩ Ϫ 2 C2Ph Ϫ Cu Ϫ 3], 1047 (12)
[Mϩ Ϫ 3 C2Ph Ϫ Cu Ϫ 3], 785 (23) [(PEt3)Cp*Rh(C2Ph)3Cu2ϩ],
621 (100) [(PEt3)Cp*Rh(C2Ph)2Cuϩ].
Complex 6 could also be obtained, albeit in lower yield (0.09 g,
58% based on Rh), by carrying out the reaction starting from
[RhCp*Cl2]2 (0.09 g, 0.15 mmol) and [cis-Pd(C6F5)2(thf)2] (0.17 g,
0.30 mmol) (molar ratio 1:2) and following the same procedure as
described for 5.
10: (0.05 g, 22%). Ϫ C60H50Ag2F10PPtRh (1505.77): calcd. C 47.86,
H 3.35; found C 47.33, H 3.35. Ϫ IR: ν˜ ϭ 2053 (s br), 2020 (sh)
cmϪ1 (CϵC); 797 (s), 778 (s) cmϪ1 (C6F5)xϪsens. Ϫ 1H NMR
(CDCl3): at 20 °C: δ ϭ 0.90 (m, 9 H, CH3, PEt3), 1.81 (m, 6 H,
CH2, PEt3), 1.86 (d, 4JPϪH ϭ 1.7, 15 H, Cp*), 7.17, 7.05, 6.92, 6.77
(m, 20 H, Ph). Ϫ 19F NMR (CDCl3): at 20 °C: δ ϭ Ϫ165.91 (m, 4
Synthesis of [Cp*Ir(µ-Cl3)IrCp*]2[(C6F5)2MЈ(µ-Cl2)MЈ(C6F5)2]
(MЈ ؍ Pt 7, Pd 8): Complexes 7 and 8 were prepared in a manner
similar to that described for 5. Reagents and quantities used:
[IrCp*Cl2]2 (0.10 g, 0.13 mmol) and [cis-Pt(C6F5)2(thf)2] (0.09 g,
0.13 mmol) for 7; [IrCp*Cl2]2 (0.08 g, 0.10 mmol) and [cis-
Pd(C6F5)2(thf)2] (0.06 g, 0.10 mmol) for 8 (molar ratio 1:1). They
were obtained as yellow solids.
3
Fm), Ϫ164.78 (t, 2 Fp), Ϫ114.28 (d, JPtϪF ϭ 394.9, 4 Fo). Ϫ 31P
NMR (CDCl3): at 20 °C: δ ϭ 37.18 (d, 1JRhϪP ϭ 119.3). Ϫ FAB(Ϫ)
Ϫ
MS: m/z (%) ϭ 1786 (23) [Pt2(C6F5)4(C2Ph)4Ag3 Ϫ 1], 1604 (4)
[MϪ ϩ C2Ph Ϫ 3], 630 (24) [Pt(C6F5)2(C2Ph)Ϫ], 441 (100) [RhCp*
Ϫ
7: (0.13 g, 78%). Ϫ C64H60Cl8F20Ir4Pt2 (2651.86): calcd. C 28.99,
H 2.28; found C 28.71, H 2.45. Ϫ IR: ν˜ ϭ 810 (s), 798 (s) cmϪ1
(C6F5)xϪsens; 290 (m), 261 (m) cmϪ1 (MϪCl). Ϫ 1H NMR ([D6]ace-
tone): at 20 °C: δ ϭ 1.77 (s, Cp*). Ϫ 19F NMR ([D6]acetone): at
20 °C: δ ϭ Ϫ167.89 (m, 8 Fm), Ϫ166.91 (t, 4 Fp), Ϫ117.47 (d,
3JPtϪF ϭ 526.4, 8 Fo). Ϫ ES(ϩ) MS: m/z (%) ϭ 761 (100) [Ir2Cp*2-
Cl3ϩ]. Ϫ ES(Ϫ) MS: m/z (%) ϭ 565 (42) [Pt(C6F5)2ClϪ].
(C2Ph)2 ϩ 1].
11: (0.14 g, 61%). Ϫ C60H50Cu2F10IrPPt (1506.44): calcd. C 47.84,
H 3.34; found C 47.43, H 3.17. Ϫ IR: ν˜ ϭ 2006 (s), 1969 (s) cmϪ1
(CϵC); 798 (s), 778 (s) cmϪ1 (C6F5)xϪsens. Ϫ 1H NMR (CDCl3): at
20 °C: δ ϭ 0.86 (m, 9 H, CH3, PEt3), 1.89 (m, 6 H, CH2, PEt3), 2.06
(s, 15 H, Cp*), 7.16Ϫ7.08 (m, 20 H, Ph). Ϫ 19F NMR (CDCl3): at
20 °C: δ ϭ Ϫ165.95 (m, 4 Fm), Ϫ164.89 (t, 2 Fp), Ϫ115.82 (d,
3JPtϪF ϭ 378.4, 4 Fo). Ϫ 31P NMR (CDCl3): at 20 °C: δ ϭ Ϫ7.57
(s). Ϫ FAB(ϩ) MS: m/z (%) ϭ 1507 (4) [Mϩ ϩ 1], 1405 (10) [Mϩ
Ϫ C2Ph], 1337 (6) [Mϩ Ϫ C6F5 Ϫ 2], 1238 (18) [Mϩ Ϫ C2Ph Ϫ
C6F5], 711 (80) [Pt(C6F5)2Cu(PEt3)], 593 (82) [Pt(C6F5)2Cu], 463
(100) [Pt(C6F5)].
8: (0.1 g, 79%). Ϫ C64H60Cl8F20Ir4Pd2 (2474.52): calcd. C 31.07, H
2.44; found C 30.86, H 2.08. Ϫ IR: ν˜ ϭ 796 (s), 782 (s) cmϪ1
(C6F5)xϪsens; 287 (m), 261 (m) cmϪ1 (MϪCl). Ϫ 1H NMR ([D6]ace-
tone): at 20 °C: δ ϭ 1.77 (s, Cp*). Ϫ 19F NMR ([D6]acetone): at
20 °C: δ ϭ Ϫ166.81 (m, 8 Fm), Ϫ165.29 (t, 4 Fp), Ϫ113.28 (d, 8
Fo). Ϫ ES(ϩ) MS: m/z (%) ϭ 761 (100) [Ir2Cp*2Cl3ϩ]. Ϫ ES(Ϫ)
MS: m/z (%) ϭ 477 (42) [Pd(C6F5)2ClϪ].
12: (0.20 g, 66%). Ϫ C60H50Ag2F10IrPPt (1595.09): this complex
crystallizes with a 1/2 molecule of CH2Cl2, as observed by 1H NMR
in CDCl3. C60H50Ag2F10IrPPt·0.5CH2Cl2 requires C 44.38, H 3.14;
found C 44.29, H 3.44. Ϫ IR: ν˜ ϭ 2070 (m), 2036 (m) cmϪ1 (CϵC);
797 (m), 777 (m) cmϪ1 (C6F5)xϪsens. Ϫ 1H NMR (CDCl3): at 20 °C:
δ ϭ 0.88 (m, 9 H, CH3, PEt3), 1.86 (m, 6 H, CH2, PEt3), 1.94 (s,
15 H, Cp*), 5.33 (s, CH2Cl2), 7.14, 7.04, 6.90, 6.77 (m, 20 H, Ph).
Complexes 7 and 8 could also be obtained, albeit in lower yields
(0.05 g, 46% for 7; 0.04 g, 31% for 8, based on Ir), by carrying out
the reactions starting from [IrCp*Cl2]2 (0.07 g, 0.09 mmol) and [cis-
Pt(C6F5)2(thf)2] (0.12 g, 0.18 mmol) for 7 and [IrCp*Cl2]2 (0.08 g,
0.10 mmol) and [cis-Pd(C6F5)2(thf)2] (0.12 g, 0.20 mmol) for 8
(molar ratio 1:2), following the same procedure as described for 5.
Ϫ
19F NMR (CDCl3): at 20 °C: δ ϭ Ϫ165.87 (m, 4 Fm), Ϫ164.76
3
(t, 2 Fp), Ϫ114.34 (d, JPtϪF ϭ 387.3, 4 Fo). Ϫ 31P NMR (CDCl3):
Synthesis of [(PEt3)Cp*M(µ-1κCα:η2-CϵCPh)2MЈЈ2(µ-4κCα:η2-
CϵCPh)2Pt(C6F5)2] (M ؍ Rh, MЈЈ ؍ Cu 9, MЈЈ ؍ Ag 10; M ؍ Ir,
MЈЈ ؍ Cu 11, MЈЈ ؍ Ag 12): An orange solution of [(PEt3)Cp*
Rh(µ-Cl)2Pt(C6F5)2] (1) (0.15 g, 0.16 mmol) in acetone (10 mL) was
treated with [CuCϵCPh]x (0.26 g, 1.58 mmol) and the mixture was
stirred for 2 h. The resulting yellow suspension was concentrated
to dryness, the solid residue was extracted with CH2Cl2 (30 mL),
and the extract was filtered through Celite to eliminate the excess
[CuCϵCPh]x and the CuCl formed. The resulting yellow solution
was concentrated to dryness and the residue was treated with cold
Et2O (5 mL) to yield complex 9 as a yellow solid. Complexes
10؊12 were similarly prepared, also as yellow solids. In the case of
complex 10, the pale-brown solid thus obtained was recrystallized
from acetone/Et2O to give 10 as a pure yellow solid; in the case of
complex 12, the solid residue was treated with acetone instead of
diethyl ether. Reagents and quantities used: 1 (0.15 g, 0.16 mmol)
and [AgCϵCPh]x (0.15 g, 0.72 mmol) for 10; [(PEt3)Cp*Ir(µ-
at 20 °C: δ ϭ Ϫ5.4 (s). Ϫ FAB(ϩ) MS: m/z (%) ϭ 1159 (9)
[(PEt3)Cp*Ir(C2Ph)3Ag2Ptϩ], 965 (11) [(PEt3)Cp*Ir(C2Ph)3Ag2ϩ Ϫ
ϩ
1], 846 (15) [Cp*Ir(C2Ph)3Ag2
Ϫ 1], 755 (55) [(PEt3)Cp*
Ir(C2Ph)2Agϩ], 637 (100) [Cp*Ir(C2Ph)2Agϩ].
X-ray Crystal Structure Determinations: Suitable crystals of
1·Me2CO, 6, and 9·CH2Cl2 were obtained by slow diffusion of hex-
ane into acetone (1, 6) or CH2Cl2 (9) solutions of these complexes
at Ϫ30 °C. Relevant crystal data are listed in Table 5. Intensity
data for 1·Me2CO and 6 were collected on a Siemens P4 four-circle
diffractometer and cell constants were calculated from 30
reflections (1·Me2CO) or 52 reflections (6) with 2θ angles ranging
from 24 to 26°. Intensity data for 9·CH2Cl2 were collected on a
Siemens/STOE AED4 four-circle diffractometer and cell constants
were refined from 2θ values of 36 reflections (22.5 Ͻ 2θ Ͻ 31.7°).
An absorption correction based on azimuthal data was applied;
transmission coefficients were in the range 1.000 to 0.677
1638
Eur. J. Inorg. Chem. 2001, 1631Ϫ1640

Synthesis of Novel Heterotetrametallic Polyalkynyl Complexes
FULL PAPER
Table 5. Crystal data and structure refinement parameters for 1·Me2CO, 6, and 9·CH2Cl2 (wR2 ϭ [Σ w(F2o Ϫ Fc2)2/Σ wF4o]0·5; R1 ϭ
Σ|Fo| Ϫ |Fc|/Σ|Fo|)
1·Me2CO
6
9·CH2Cl2
Empirical formula
Molecular mass
Temperature [K]
C28H30Cl2F10PPtRh·Me2CO
C64H60Cl8F20Pd2Rh4
C60H50Cu2F10PPtRh·CH2Cl2
1014.47
200
0.71073
Monoclinic
P21/n
10.439(1)
14.611(1)
11.285(1)
90
2117.16
200
0.71073
1501.98
173
˚
Wavelength [A]
0.71073
Triclinic
Crystal system
Space group
Orthorhombic
Pca21
14.820(5)
17.993(6)
28.296(9)
¯
P1
˚
a [A]
10.963(3)
13.052(4)
20.643(6)
93.44(2)
99.29(2)
106.03(2)
2784.7(13)
2
1.791
3.747
˚
b [A]
˚
c [A]
α [deg]
β [deg]
γ [deg]
90
90
90
7545(4)
93.15(1)
90
1718.6(3)
2
1.960
4.827
3
˚
Volume [A ]
Z
4
Density (calcd.) [g/cm3]
Absorption coeff. [mmϪ1
F(000)
1.864
1.692
4128
]
984
1476
Crystal dimensions [mm]
θ range [°]
0.52 ϫ 0.50 ϫ 0.36
2.28 to 24.00
Ϫ1 Յ h Յ11
Ϫ1 Յ k Յ 16
Ϫ12 Յ l Յ 12
3582
0.48 ϫ 0.44 ϫ 0.24
2.26 to 25.01
Ϫ1 Յ h Յ 17
Ϫ1 Յ k Յ 21
Ϫ1 Յ l Յ 33
8134
0.30 ϫ 0.23 ϫ 0.19
2.01 to 25.00
0 Յ h Յ 13
Ϫ15 Յ k Յ 14
Ϫ24 Յ l Յ 24
10352
Index ranges
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
2802 [R(int) ϭ 0.0234]
7058 [R(int) ϭ 0.0423]
Full-matrix least-squares on F2
6587/1/884
1.025
9795 [R(int) ϭ 0.0374]
2763/0/226
1.080
R1 ϭ 0.0239
wR2 ϭ 0.0585
R1 ϭ 0.0274
wR2 ϭ 0.0643
0.581 and Ϫ1.080
9792/2/737
1.017
R1 ϭ 0.0464
wR2 ϭ 0.0893
R1 ϭ 0.0935
wR2 ϭ 0.1119
1.86 and Ϫ0.81
R1 ϭ 0.0380
wR2 ϭ 0.0682
R1 ϭ 0.0714
wR2 ϭ 0.1858
0.562 and Ϫ0.749
R indices (all data)
Ϫ3
˚
Largest diff. peak and hole [e·A
]
(1·Me2CO), 0.974 to 0.704 (6), and 1.000 to 0.669 (9·CH2Cl2). The
structures were solved by Patterson (1, 9) or direct (6) methods
and refined against F2 using the program SHELXL-93.[27] All non-
hydrogen atoms were assigned anisotropic displacement parameters
and were refined without positional constraints, except for the dis-
ordered carbon atoms of one of the ethyl groups of the PEt3 ligand
in 9·CH2Cl2 (see below), for which the interatomic distances were
Acknowledgments
´
We thank the Direccion General de Ensen˜anza Superior, Spain
(Project PB 98-1595-C02-01,02) and the Universidad de La Rioja
(Project API-00/B17) for their financial support.
[1] [1a]
N. Wheatley, P. Kalck, Chem. Rev. 1999, 99, 3379. Ϫ [1b] D.
W. Stephan, T. T. Nadasdi, Coord. Chem. Rev. 1996, 147, 147.
Ϫ
˚
restrained to be 1.54 A. A phenyl ring of one phenylacetylide ligand
[1c]
R. M. Bullock, C. P. Casey, Acc. Chem. Res. 1987, 20,
was found to be disordered over two positions, which were refined
with partial occupancy factors of 0.5/0.5. One methyl carbon atom
of the PEt3 ligand was found to be disordered over two positions,
which were refined with partial occupancy factors of 0.67/0.33. In
all three structures, all hydrogen atoms were constrained to ideal-
ized geometries and were assigned a refined isotropic displacement
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