New Rh derivatives of s-indacene active in dehydrogenative silylation of styrene
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Date
2006
Journal Title
Journal ISSN
Volume Title
Publisher
ELSEVIER SCIENCE SA
Abstract
The mono- and bimetallic complexes [(2,6-diethyl-4,8-dimethyl-s-indacenide){Rh(COD)}] (1), anti-[(2,6-diethyl-4,8-dimethyl-s-indacenediide) {Rh(COD)}(2)] (2a), syn-[(2,6-diethyl-4,8-dimethyl-s-indacenediide){Rh(COD)}(2)] (2b) were synthesized and characterized spectroscopically and in the case of complex 2b, by means of X-ray diffraction. The C-13 and Rh-103 NMR studies suggest that the bonding mode of the indacenediide ligand can be described as intermediate between eta(3)- and eta(5)-coordination. This result was confirmed by the crystal structure of 2b as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed a strong intermetallic communication through the fused ring ligand. This property was further illustrated by higher activity and selectivity of binuclear complexes 2 for the catalytic dehydrogenative silylation of styrene. (c) 2006 Elsevier B.V. All rights reserved.
Description
Keywords
rhodium complex, s-indacene, silylation, METAL-METAL INTERACTIONS, ORGANOMETALLIC COMPLEXES, CRYSTAL-STRUCTURE, IR(I) COMPLEXES, REACTIVITY, PENTALENE, LIGANDS, RH(I), BINUCLEAR, BEHAVIOR