Synthesis of the Reagent [Na][Pt(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] and Preparation of the Platinacarborane Complexes [PtX(PEt₃)₂(η⁵-7-CB₁₀H₁₁)] (X = H, Au(PPh₃), Cu(PPh₃), HgPh)

The salt [Na][Pt(PEt 3 ) 2 (η 5 -7-CB 10 H 11 )] ( 1a ) has been prepared. Protonation affords the hydrido complex [PtH(PEt 3 ) 2 (η 5 -7-CB 10 H 11 )] ( 2 ) while reactions with [AuCl(PPh 3 )], [CuCl(PPh 3 )] 4, and [HgClPh] yield the dimetal compounds [PtM(PEt 3 ) 2 (PPh 3 )(η 5 -7-CB 10 H 11 )] ( 3a, M = Au; 3b, M = Cu) and [PtHgPh(PEt 3 ) 2 (η 5 -7-CB 10 H 11 )] ( 3c ), respectively. The salt [N(PPh 3 ) 2 ][Pt(CO)(PPh 3 )(η 5 -7-CB 10 H 11 )] ( 4 ) has also been obtained. Single-crystal X -ray diffraction studies have been made on 2 and 3a − c . Complexes 2, 3a, and 3c have similar molecular structures with H, Au(PPh 3 ), and HgPh groups, respectively, σ-bonded to the Pt of the Pt(PEt 3 ) 2 (η 5 -7-CB 10 H 11 ) group. In 3b, however, the copper atom of the Cu(PPh 3 ) moiety is attached to the Pt(PEt 3 ) 2 (η 5 -7-CB 10 H 11 ) fragment both by a Pt−Cu σ-bond and by two exopolyhedral B−H⇀Cu donor bonds from BH groups in the open face of the nido -7-CB 10 H 11 cage ligating the platinum. The structure of the salt 4 has also been determined by X -ray diffraction.