Synthesis, structure and reactivity of a novel monocarbon hydridorhodacarborane closo-2,2-(ph3p)2-2-h-1-(me3n)-2,1 - rhcb10h10 molecular structure of 16-electron closo-2-(ph3p)-2-cl-1-(me3n)-2,1 - rhcb10h10

Article abstract of DOI:10.1016/S0022-328X(96)06724-1

A novel 12-vertex monocarbon hydridorhodacarborane closo-2,2-(Ph₃P)₂-2-H-1-(Me₃N)-2,1-RhCB₁₀H₁₀ 1 has been synthesized by the reaction of Rh(PPh₃)₃Cl (2) with nido-B₁₀H₁₂CNMe₃ (3) under alkaline conditions. At low temperature 1 exists as a mixture of two preferred conformers in solution, both having C_s symmetry, in accord with the hindered rotation of the (Ph₃P)₂RhH vertex with respect to the CB₄ face of the monocarbon carborane cage. Complex 1 readily reacts with chlorine-containing reagents to form mononuclear 16-electron closo-2-(Ph₃P)-2-Cl-1-(Me₃N)-2,1-RhCB₁₀H₁₀ (5), whose structure was unambiguously confirmed by an X-ray diffraction study. The results of an X-ray diffraction study of the closely related dicarbon carborane derivative closo-3,3-(Ph₃P)₂-3-Cl-3,1,2-RhC₂B₉H₁₁ (10), prepared from closo-3,3-(Ph₃P)₂-3-H-3,1,2-RhC₂B₉H₁₁ by analogy with 5, are also reported.