Abstract
Reactions of the rhodium(II) dimer [(dbpb)Rh]2 (1) ((dbpb)H2 (2) = 4,5-dimethyl-1,2-bis((4-(1-butylpentyl))pyridine-2-carboxamido)benzene) with H2, CO, and CH2CH2 produce a rhodium(III) hydride, (dbpb)Rh−H (3), dirhodium ketone, (dbpb)Rh−C(O)−Rh(dbpb) (4), and an ethylene-bridged complex, (dbpb)Rh−CH2CH2−Rh(dbpb) (5), respectively. The rhodium(III) hydride (3) reacts with CO and H2CO to produce formyl, (dbpb)Rh−CHO (6), and hydroxymethyl, (dbpb)Rh−CH2OH (7) complexes. Equilibrium thermodynamic studies for reactions of 1 with hydrogen and ethene and the observed substrate reactions of 1 and 3 indicate that the (dbpb)Rh−H and (dbpb)Rh−C bond dissociation enthalpies are comparable to those for rhodium porphyrin complexes.
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