The reaction of the 16-electron “pseudo-aromatic” complex Cp*Ir[Se2C2(B10H10)] (1, Cp* = η5-C5Me5) with [Ir(cod)(µ-OC2H5)]2 leads to the trinuclear iridium complexes {(cod)Ir[Se2C2(B10H8)(OC2H5)]}Ir{[Se2C2(B10H10)]IrCp*} (2), {(cod)Ir[Se2C2(B10H8)(OC2H5)]}Ir{[Se2C2(B10H9)]IrCp*} (3), {Cp*Ir[Se2C2(B10H9)]}{IrSe2[C2(B10H9)(OC2H5)]}{[Se2C2(B10H10)] IrCp*} (4) and one mononuclear complex Cp*Ir[Se2C2(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 Ir3 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–Bcluster: {Cp*Ir[Se2C2(B10H9)]}, O–Bcluster: {[Se2C2(B10H9)](OC2H5)}, and intact carborane: {Cp*Ir[Se2C2 (B10H10)]}) without the presence of a metal–metal bond. Analogous reaction of 1 with [Ir(cod)(µ-OCH3)]2 results in formation of the trinuclear complex {Cp*Ir[Se2C2(B10H9)]}{IrSe2[C2(B10H9)(OCH3)]}{[Se2C2(B10H10)]IrCp*} (6) and mononuclear complex Cp*Ir[Se2C2(B10H8)(OCH3)2] (7). The structures of 2, 3, 4, 5, 6 and 7 have been determined by crystallographic studies.
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