Pincer-type complexes with B(3)-H selective bond activation of m-carborane

Herein, we describe the synthesis of a series pincer-type half-sandwich complexes containing selective B(3)-H activation of m-carborane. Four pincer-type complexes containing Cp*M (M = Ir/Rh) and (& eta;6-pcym)Ru metalcorner, ionic Cp*M[m-C2B10H9(CS2CH3)2](CF3SO3) (M = Ir (2), Rh (3)), (& eta;6-pcym)Ru[m-C2B10H9(CS2CH3)2] (CF3SO3) (4) and neutral solvolysis product Cp*Ir[m-C2B10H9(CS2CH3)(COS)] (Complex 5), have been prepared. The addition reaction of MeO- toward 2 3 and 4 causes the formation of moderately stable neutral unsymmetrical pincer-type complexes Cp*M{m-C2B10H9(CS2CH3)[CS(SCH3)(OCH3)]} (M = Ir (6), Rh (7)) and (& eta;6pcym)Ru{m-C2B10H9(CS2CH3)[CS(SCH3)(OCH3)]} (8). The substitution reaction of 2 3 and 4 have also been also explored, unsymmetrical chelate complexes Cp*M(tBuNC)[m-C2B10H9(CS2CH3)2](BPh4) (M = Ir (9), Rh (10)) can be obtained by using tBuNC and NaBPh4. All of these complexes have been characterized, including X-Ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.