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Dinuclear Pentamethylcyclopentadienyl Rhodium and Iridium Complexes
Containing 1,1’-Ferrocene Dichalcogenido Bridges.
X-Ray Structure Analysis of the Dimer {Cp*Ir[(SeC
5
H
4
)
2
Fe]}
2
Max Herberhold
a
*, Guo-Xin Jin
b
, and Arnold L. Rheingold
c
a
Bayreuth, Laboratorium für Anorganische Chemie der Universität
b
Shanghai, China, Chemistry Department, Fudan University
c
Newark, Delaware/USA, Department of Chemistry, University of Delaware
Received May 15th, 2002.
Dedicated to Professor Rüdiger Mews on the Occasion of his 60
th
Birthday
Abstract. The reaction of [Cp*RhCl
2
]
2
with dilithium 1,1’-ferrocene
dichalcogenolates, Fe(C
5
H
4
ELi)
2
, in THF solution led to dirho-
dium compounds, Cp*
2
Rh
2
[µ-(EC
5
H
4
)
2
Fe] (E ⫽ S(1a), Se (1b)and
Te (1c)) containing a metal-metal bond. On the other hand, dimeric
complexes {Cp*Ir[µ-(EC
5
H
4
)
2
Fe]}
2
(E ⫽ S(3a), Se (3b)) without
direct Ir···Ir interaction were obtained in low yields in the corre-
sponding reaction of [Cp*IrCl
2
]
2
, although they were prepared
more efficiently by phosphane elimination from Cp*
Ir(PPh
3
)[(EC
5
H
4
)
2
Fe] (E ⫽ S(4a), Se (4b)) using elemental sulfur
Zweikernige Pentamethylcyclopentadienyl Rhodium- und Iridium-Komplexe mit
1,1’-Ferrocen-dichalcogenido-Brücken. Röntgenstrukturanalyse des Dimeren
{Cp*Ir[(SeC
5
H
4
)
2
Fe]}
2
Inhaltsübersicht. Die Reaktion von [Cp*RhCl
2
]
2
mit Dilithium-
1,1’-ferrocen-dichalcogenolaten, Fe(C
5
H
4
ELi)
2
, in THF-Lösung
führte zu Dirhodium-Verbindungen, Cp*
2
Rh
2
[µ-(EC
5
H
4
)
2
Fe] (E ⫽
S(1a), Se (1b) und Te (1c)), die eine Metall-Metall-Bindung enthal-
ten. Dagegen wurden bei der entsprechenden Umsetzung von [Cp*
IrCl
2
]
2
in geringer Ausbeute dimere Komplexe {Cp*Ir[µ-
(EC
5
H
4
)
2
Fe]}
2
(E ⫽ S(3a), Se (3b)) ohne Ir···Ir Wechselwirkung
gebildet, die sich jedoch effektiver durch Eliminierung des Phos-
1 Introduction
1,1’-Ferrocene dithiolate complexes (containing the dianion
[Fe(C
5
H
4
S)
2
]
2⫺
as chelate ligand) are presently studied as
models for possible heterodinuclear Fe 씮 M bonding, since
the palladium(II) and platinum(II) compounds
[Fe(C
5
H
4
S)
2
]M(PPh
3
) had been shown to contain a rela-
tively short (< 300 pm) dative Fe 씮 M bond in a distorted
sandwich structure.
* Prof. Dr. M. Herberhold
Laboratorium für Anorganische Chemie der Universität Bayreuth
Postfach 101251
D-95440, Bayreuth
FAX: (49)-921-552157
e-mail: Max.Herberhold@uni-bayreuth.de
Z. Anorg. Allg. Chem. 2002, 628, 1985⫺1990 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/1985⫺1990 $ 20.00⫹.50/0 1985
(to give SPPh
3
). The complexes were characterized on the basis of
EI-mass as well as
1
Hand
13
C NMR spectra, and the molecular
structure of 3b was determined. The iridium atoms in 3b bear a
Cp* ring and are connected with three selenium atoms (⫺ two of
which are bridging ⫺) in a pseudo-tetrahedral halfsandwich ar-
rangement.
Keywords: Rhodium; Iridium; Ferrocene derivatives; Dichalcogeno-
late bridges; Sulfur; Selenium; Tellurium
phans aus Cp*Ir(PPh
3
)[(EC
5
H
4
)
2
Fe] (E ⫽ S(4a), Se (4b)) (mit Hilfe
von elementarem Schwefel unter Bildung von SPPh
3
) darstellen lie-
ßen. Die Komplexe wurden anhand der EI-Massenspektren sowie
der
1
H- und
13
C-NMR-Spektren charakterisiert, und die Molekül-
struktur von 3b wurde bestimmt. Die Iridium-Atome in 3b tragen
einen Cp* Ring und sind mit drei Selen-Atomen (⫺ davon zwei
brückenständigen ⫺) in einer pseudo-tetraedrischen Halbsand-
wich-Anordnung verbunden.
However, the substitution of two chloro ligands for a
1,1’-ferrocene dithiolate dianion generally leads to products
with long (> 400 pm) Fe···M separations [3]. We have earlier
described [4] the rhodium and iridium halfsandwich com-
plexes Cp*M(L)[(EC
5
H
4
)
2
Fe] in which the metal bears a