title: Hydride-rhodium(III)-N-heterocyclic carbene catalysts for vinyl-selective H/D exchange: a structure-activity study.
abstract: A series of neutral and cationic Rh(III) -hydride and Rh(III) -ethyl complexes bearing a NHC ligand has been synthesized and evaluated as catalyst precursors for H/D exchange of styrene using CD(3)OD as a deuterium source. Various ligands have been examined in order to understand how the stereoelectronic properties can modulate the catalytic activity. Most of these complexes proved to be very active and selective in the vinylic H/D exchange, without deuteration at the aromatic positions, displaying very high selectivity toward the β-positions. In particular, the cationic complex [RhClH(CH(3)CN)(3)(IPr)]CF(3)SO(3) showed excellent catalytic activity, reaching the maximum attainable degree of β-vinylic deuteration in only 20 min. By modulation of the catalyst structure, we obtained improved α/β selectivity. Thus, the catalyst [RhClH(κ(2)-O,N-C(9)H(6)NO)(SIPr)], bearing an 8-quinolinolate ligand and a bulky and strongly electron-donating SIPr as the NHC, showed total selectivity for the β-vinylic positions. This systematic study has shown that increased electron density and steric demand at the metal center can improve both the catalytic activity and selectivity. Complexes bearing ligands with very high steric hindrance, however, proved to be inactive.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea, Universidad de Zaragoza - CSIC, C/Pedro Cerbuna 12, 50009 Zaragoza (Spain). dgandrea@unizar.es.
authors.forename: Andrea
authors.initials: A
authors.lastname: Di Giuseppe
authors.forename: Ricardo
authors.initials: R
authors.lastname: Castarlenas
authors.forename: Jesús J
authors.initials: JJ
authors.lastname: Pérez-Torrente
authors.forename: Fernando J
authors.initials: FJ
authors.lastname: Lahoz
authors.forename: Luis A
authors.initials: LA
authors.lastname: Oro
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D003903:Deuterium / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008968:Molecular Conformation; D012238:Rhodium / Q000737:chemistry*; D013329:Structure-Activity Relationship; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D014753:Vinyl Compounds; C030011:carbene; D006859:Hydrogen; D003903:Deuterium; D012238:Rhodium; D008697:Methane
keywords: H/D exchange; N-heterocyclic carbenes; alkenes; deuteration; rhodium