Synthesis and characterization of heterometallic M-Ru (M = Co, Rh, Ir) clusters containing the nido-dicarborane-1,2-dithiolato chelating ligand.

The 16-electron half-sandwich complexes CpM[S(2)C(2)(B(10)H(10))] (M = Ir (1), Rh (2), Co (3)) react with Ru(COD)Cl(2) under basic conditions at 35-40 degrees C to give different hetero-dinuclear clusters {CpM[S(2)C(2)(B(9)H(10))]}Ru(COD) (M = Ir (1a), Rh (2a), Co (3a)) and {CpM[S(2)C(2)(B(9)H(9))]}Ru(COD)(OCH(3)) (M = Ir (1b), Rh (2b), Co (3b)) with open carborane cages. Moreover, B-H-->Ru bridge bonds were observed in complexes 1a, 2a,3a . In reaction a, minor products trinuclear complex {CpIr[S(2)C(2)(B(10)H(10))]}(2)Ru (1c) and methoxyl-disubstituted complex CpIr[S(2)C(2)(B(10)H(8))(OCH(3))(2)] (1d) were successfully isolated. However, when the reaction temperature decreased to 0-10 degrees C, the kinetically-controlled products, mono-substituted complex CpIr[S(2)C(2)(B(10)H(9))(OCH(3))] (1e) and disubstituted complex CpIr[S(2)C(2)(B(10)H(8))(OCH(3))(2)] (1d), were isolated as the main products; nevertheless, the thermodynamically-controlled products, open-carborane complexes 1a and 1b , were isolated as the minor products. In complex CpCo[S(2)C(2)(B(9)H(10))]Ru(C(7)H(8)) (3c), one COD coordinated to ruthenium has been replaced by toluene. The reactions demonstrate that different types of products can be obtained by controlling the reaction conditions. All these new complexes have been characterized by IR, (1)H NMR, (11)B NMR and elemental analyses. The molecular structures of 1a, 1b, 1c, 1d, 1e, 2a and 3a have also been determined by single-crystal X-ray diffraction analyses.