Inorg. Chem. 2003, 42, 2988−2991
Synthesis and Characterization of Mononuclear Iron Silanethiolato
Complexes Containing an Unsupported Fe−S−Si Bond System: X-ray
Crystal Structure of CpFe(CO)2SSiPh3 and Its Reaction with SO
2
,†
Istva´n Kova´cs,† Francine Be´langer-Garie´py,‡ and Alan Shaver*
Department of Chemistry, McGill UniVersity, 801 Sherbrooke Street West, Montreal,
QC H3A 2K6, Canada, and De´partement de Chimie, UniVersite´ de Montre´al, C.P. 6128,
Succ. Centre-Ville, Montre´al, QC H3C 3J7, Canada
Received February 4, 2003
Mononuclear iron silanethiolato complexes of the type CpFe(CO)2SSiR , where R ) Ph (1a) and iPr (1b), were
3
prepared via treatment of [CpFe(CO)2(THF)]BF with LiSSiPh3‚Et2O and NaSSiiPr3, respectively. The molecular
4
structure of 1a was determined by X-ray crystallography. Complex 1a was reacted with 1 equiv of SO to give the
2
corresponding O-silyl thiosulfite, CpFe(CO)2SS(O)OSiPh3 (2), via 1,2-insertion of SO into the S−Si bond. This
2
reaction models the activation of SO in the homogeneously catalyzed Claus process.
2
Introduction
majority of these studies utilized group 11 and 12 post-
transition metals only, well-characterized silanethiolato
complexes of the common transition metals remain relatively
rare.2-4,7-10 As recent advances in the chemistry of
silanethiolates7-14 suggest, there is current interest in devel-
oping synthetic pathways via silanethiolates to sulfur-
containing metal clusters that could be useful as catalysts or
new materials, as well as in developing catalytic models
based directly on silanethiolates. These applications require
primarily complexes of the catalytically important transition
metals with an unsupported silanethiolate ligand, where the
M-S-Si bond system can be fine-tuned by selecting the
appropriate metal, ligands, and substituents at silicon.
Silanethiolato complexes have been studied for two
decades for their relevance to well-known alkane(arene)-
thiolate or trialkyl(aryl)siloxide complexes, with particular
emphasis on their structural diversity.1-6 However, since the
* Corresponding author. Fax: (514) 398-3797. E-mail: alan.shaver@
mcgill.ca
† McGill University.
‡ Universite´ de Montre´al.
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2988 Inorganic Chemistry, Vol. 42, No. 9, 2003
10.1021/ic030049g CCC: $25.00 © 2003 American Chemical Society
Published on Web 04/01/2003