Synthesis and reactivity of 1,2-bis(chlorodimethylgermyl)carborane and 1,2-bis(bromodimethylstannyl)carborane

Article abstract of DOI:10.1021/ic0110878

The 1,2-bis(chlorogermyl)-(1) and 1,2-bis(bromostannyl)carborane (2) have been prepared by the reaction of dilithio-o-carborane with Me₂GeCl₂ and Me₂SnBr₂, respectively. Compounds 1 and 2 are found to be good precursors for the synthesis of a variety of cyclization compounds. The Wurtz-type coupling reaction of 1 and 2 using sodium metal afforded the four-membered digerma compound 3 and five-membered tristanna compound 4, respectively. The salt elimination reactions of 1 and 2 using Li₂N^tBu and Li₂PC₆H₅ afforded the cyclic products (Me₂)M(C₂B₁₀H₁₀) M(Me₂)E (5, M = Ge, E = N^tBu; 6, M = Sn, E = N^tBu; 7, M = Ge, E = PC₆H₅; 8, M = Sn, E = PC₆H₅). The 1,2-bis(dimethylgermyl)carborane 9 and 1,2-bis(dimethylstannyl)carborane 10 were prepared by the reaction of 1 and 2 with sodium cyanoborohydride. The reactions of 9 and 10 with Pd(PPh₃)₄ afforded the bis(germyl)palladium 12 and bis(stannyl)palladium 13 complexes, respectively.