Palladium-mediated substitution of the closo-B12H12(−2) and nido-7,8-C2B9H12(−1) ions by PMe2Ph: The single-crystal structure studies of 1,7-(PMe2Ph)2-closo-B12H10 and 9-PMe2Ph-nido-7,8-C2B9H11

Treatment of Na2[closo-B12H12] with one mole equivalent of (PMe2Ph)2PdCl2 in THF at room temperature formed Na[closo-(PMe2Ph)-B12H11], 1,7- and 1,12-(PMe2Ph)2-closo-B12H10 in moderate yield. Reaction of K[nido-7,8-C2B9H12] with one half a mole equivalent of (PMe2Ph)2PdCl2 in CH2Cl2 at room temperature formed a mixture of 9-PMe2Ph-nido-7,8-C2B9H11 and 10-PMe2Ph-nido-7,8-C2B9H11 in overall good yield. Single-crystal X-ray structures of 1,7-(PMe2Ph)2-closo-B12H10 and 9-PMe2Ph-nido-7,8-C2B9H11 are reported.

Palladium-mediated phosphine derivatization of borane anions was demonstrated using the reagent (PMe2Ph)2PdCl2 (1). Treatment of icosahedral borane anion [closo-B12H12]2− with (1) formed three phosphine derivatives: [(PMe2Ph)-closo-B12H11]−, 1,7-(PMe2Ph)2-closo-B12H10, and 1,12-(PMe2Ph)2-closoB12H10, in moderate yield. Reaction of [nido7,8-C2B9H12]− with 1 similarly formed two phosphine derivatives: 9-PMe2Ph-nido-7,8-C2B9H11 and 10-PMe2Ph-nido-7,8-C2B9H11, in overall good yield.Figure optionsDownload as PowerPoint slide