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The Way into the Bridge: A New Bonding Mode of Tertiary Phosphanes, Arsanes, and Stibanes
Author(s) -
Werner Helmut
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200300627
Subject(s) - chemistry , transition metal , carbene , molecule , monomer , stereochemistry , ligand (biochemistry) , bridging ligand , metal , crystallography , polymer chemistry , organic chemistry , polymer , catalysis , receptor , biochemistry
Abstract Until recently, tertiary phosphanes, arsanes, and stibanes were considered to bind to transition‐metal centers only in a terminal coordination mode. Investigations on the reactivity of square‐planar trans ‐[RhCl(CRR′)(L) 2 ] compounds revealed that compounds in which L=Sb i Pr 3 can be converted upon heating into dinuclear complexes [Rh 2 Cl 2 (μ‐CRR′) 2 (μ‐Sb i Pr 3 )] with the carbene and stibane ligands in bridging positions. Although attempts to replace the stibane in these complexes with a tertiary arsane or phosphane failed, substitution of the chloro ligands for acetylacetonates followed by bridge–ligand exchange allowed the preparation of the phosphane‐ and arsane‐bridged compounds [Rh 2 (acac) 2 (μ‐CRR′) 2 (μ‐PR 3 )] and [Rh 2 (acac) 2 (μ‐CRR′) 2 (μ‐AsMe 3 )]. The acac ligands can be replaced by anionic Lewis bases to give either monomeric [Rh 2 X 2 (μ‐CRR′) 2 (μ‐ER 3 )] or dimeric chain‐like [XRh(μ‐CRR′) 2 (μ‐ER 3 )Rh(μ‐X) 2 Rh(μ‐CRR′) 2 (μ‐ER 3 )RhX] molecules.