Synthesis and Coordination Chemistry of a Chelating P–Sn Ligand Based on Stanna-closo-dodecaborate

Substitution at a B–H unit of the heteroborate cluster stanna-closo-dodecaborate [SnB₁₁H₁₁]^2– at the upper belt of the icosahedron by one of the triarylphosphine moieties of xantphos was carried out under the catalysis of palladium acetate. The resulting coupling product is a monoanion offering two coordination sites: a low-valent tin-cluster vertex and a triaryl phosphine moiety. The basicity and nucleophilicity of the anion were investigated in reactions with a strong acid or an alkylating agent. Transition-metal electrophiles like platinum halide PtCl₂ or rhodium carbonyl [Rh(CO)₂Cl]₂ react with the bidentate ligand, with the formation of cis-coordination products.

The heteroborate cluster [SnB₁₁H₁₁]^2– was substituted at the upper belt of the icosahedron by one of the triarylphosphine moieties of xantphos under the catalysis of palladium acetate. Transition-metal electrophiles, like the platinum halide PtCl₂ or the rhodium carbonyl [Rh(CO)₂Cl]₂, react with the bidentate ligand, with the formation of cis-coordination products.

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