Construction of trinuclear iridium clusters through ancillary ortho-carborane-1,2-diselenolato ligands, with simultaneous iridium-induced B-H activation

The reaction of the 16-electron "pseudo-aromatic" complex Cp*IrSe2C2(B10H10)] (1, Cp* = eta5-C5Me5) with Ir(cod)(micro-OC2H5)]2 leads to the trinuclear iridium complexes {(cod)IrSe2C2(B10H8)(OC2H5)]}Ir{Se2C2(B10H10)]IrCp*} (2), {(cod)IrSe2C2(B10H8)(OC2H5)]}Ir{Se2C2(B10H9)]IrCp*} (3), {Cp*IrSe2C2(B10H9)]}{IrSe(2)C2(B10H9)(OC2H5)]}{Se2C2(B10H10)] IrCp*} (4) and one mononuclear complex Cp*IrSe2C2(B10H8)(OC2H5)(2)] (5). The reactivity of 2 was investigated and revealed that transformation from 2 to 3 occurred thermally in solution. The transoid complex 2 (with the carborane diselenolato units in trans position) can be converted in nearly 90% yield to the cisoid complex 3. In complexes 2, 3, two diselenolato carborane ligands bridge the Ir(3) core, which consists of Ir-Ir metal bonds. Compared with transoid 2, the cisoid 3 contains two iridium-boron bonds. Complex 4 consists of three different coordination environment carborane ligands (Ir-B(cluster): {Cp*IrSe2C2(B10H9)]}, O-B(cluster): {Se2C2(B10H9)](OC2H5)}, and intact carborane: {Cp*IrSe2C2 (B10H10)]}) without the presence of a metal-metal bond. Analogous reaction of 1 with Ir(cod)(micro-OCH(3))](2) results in formation of the trinuclear complex {Cp*IrSe2C2(B10H9)]}{IrSe(2)C2(B10H9)(OCH3)]}{Se2C2(B10H10)]IrCp*} (6) and mononuclear complex Cp*IrSe2C2(B10H8)(OCH3)(2)] (7). The structures of 2, 3, 4, 5, 6 and 7 have been determined by crystallographic studies.