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Dicarbonylrhodium(I) Complexes of Bipyridine Ligands with Proximate H‐Bonding Substituents and Their Application in Methyl Acetate Carbonylation
Author(s) -
Conifer Christopher M.,
Law David J.,
Sunley Glenn J.,
Haynes Anthony,
Wells John R.,
White Andrew J. P.,
Britovsek George J. P.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100423
Subject(s) - chemistry , carbonylation , cationic polymerization , bipyridine , methyl acetate , solid state , medicinal chemistry , metal , stereochemistry , crystallography , catalysis , polymer chemistry , crystal structure , carbon monoxide , organic chemistry
A series of cationic cis ‐dicarbonylrhodium(I) complexes [Rh(L)(CO) 2 ]SbF 6 has been prepared containing 2,2′‐bipyridine ligands with proximate H‐bonding substituents R in the 6‐ and 6′‐position (R = OH, NH 2 , COOEt and PO(OEt) 2 ). The solid‐state structures have been determined by X‐ray crystallography for the complexes where R = OH, NH 2 and COOEt. The molecular structures have revealed metal–metal and π–π interactions between the square‐planar complexes resulting in the formation of molecular chains in the solid state. IR studies on the reaction of [Rh(bipy)(CO) 2 ]SbF 6 with MeI have shown the formation of a neutral complex [RhI(CO)(bipy)], which undergoes oxidative addition of MeI much faster than the cationic complex [Rh(bipy)(CO) 2 ] + . Although all complexes show good activities for the carbonylation of methyl acetate, this is believed to be due to their instability and the formation of [RhI 2 (CO) 2 ] – under the reaction conditions.