SELECTIVITY IN SUBSTITUTION CHEMISTRY OF MIXED-METAL, TETRAHEDRAL MCO3 (M = FE, RU) CARBONYL CLUSTERS - CO-59 NMR-STUDY AND CRYSTAL-STRUCTURE OF RUCO3(MU-3-H)(MU-CO)3(CO)8(NME3)

Reactions between tetrahedral mixed-metal clusters HMCo3(CO)12 [M = Fe (1a), M = Ru (1b)] and trimethylamine N-oxide have led to the formation of the amine-substituted clusters HMCo3(CO)11(NMe3) [M = Fe (2a), M = Ru (2b)] in high yields. Co-59 NMR and IR spectroscopy were used to study the site selectivity of these reactions and indicate that substitution of the amine for the CO ligand takes place preferentially at one of the cobalt atoms. Clusters 2 are labile in solution and transform in the corresponding anions [Me3NH][MCo3(CO)12], owing to decoordination of the amine. Substitution reactions of the amine with other 2e donor ligands (PPh3, SEt2) were also studied. Disubstituted clusters were prepared under mild conditions and the very labile HMCo3(CO)10(NMe3)2, in which two cobalt atoms carry each an amine ligand, was characterized by Co-59 NMR spectroscopy. The structure of 2b has been determined by X-ray diffraction: space group Pna2(1) with a = 16.877 (5) angstrom, b = 10.296 (2) angstrom, c = 11.946 (2) angstrom, alpha = beta = gamma = 90-degrees, and Z = 4. The structure was refined to R = 0.026 and R(w) = 0.035 on the basis of 1471 reflections having F(o)2 > 3-sigma(F(o)2). The cluster has a tetrahedral structure and the amine is axially bonded to a basal cobalt atom.