Oxidation of tricarbonylmolybdacarborane. 3. A new entry to the first examples of sulfido-bridged dinuclear molybda(V)carboranes

Abstract

[(C2B9H11)Mo(CO)(3)](2)PPN2 (2(.)PPN(2)), a new precursor for the oxidative decarbonylation reaction, was synthesized in high yield by the one-electron oxidation reaction of [(C2B9H11)Mo(CO)(3)]PPN2, 2(.)PPN(2) was structurally characterized, showing a dimeric nature with long (3.321 Angstrom) Mo-Mo bonding. Reaction of 2(.)PPN(2) with sulfur gave the completely decarbonylated product [(C2B9H11)Mo(mu-S)(S)](2)PPN2 (3(.)PPN(2)). The ligand substitution of the terminal sulfur ligands in 3(.)PPN(2) to oxygen ligands was carried out with the use of PhIO to give [(C2B9H11)Mo(mu-S)(O)](2)PPN2 (4(.)PPN(2)). The structures of 3(.)PPN(2) and 4(.)PPN(2) were also studied.