Why do cationic hydridoiridium(III) complexes with beta-aminophosphane ligands favour the transfer hydrogenation of ketones over the direct "H2-hydrogenation"?--A computational approach.
Density functional theory and ab initio molecular orbital calculations show that the observed inability of cationic hydridoiridium(III) complexes with beta-aminophosphane ligands to catalyse the direct hydrogenation of carbonyl compounds with dihydrogen ("H2-hydrogenation") in contrast to their ruthenium(II) equivalents is due to the inability of H2 to displace a coordinated solvent molecule from an intermediate hydrido complex.
Puchta
Ralph
R
Computer-Chemie Centrum (CCC), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052 Erlangen (Germany), Fax: (+49) 9131-8526565.|Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 1, 91058 Erlangen (Germany), Fax: (+49) 9131-8527387.
Dahlenburg
Lutz
L
Institut für Anorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 1, 91058 Erlangen (Germany), Fax: (+49) 9131-8527387.
Clark
Timothy
T
Computer-Chemie Centrum (CCC), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, 91052 Erlangen (Germany), Fax: (+49) 9131-8526565.|Interdisciplinary Center for Molecular Materials, Nägelsbachstr. 25, 91052 Erlangen (Germany).