LAUSR

Abstract Reaction of the thallium salt Tl[7,8-Me2-10-SMe2-7,8-nido-C2B9H8] with [(cod)RhCl]2 in THF furnishes new rhodacarborane 1,2-Me2-3,3-(cod)-8-SMe2-3,1,2-closo-RhC2B9H8 (1). The latter undergoes 1,2 → 1,7 carbon atom isomerization upon reflux in o-xylene for 5 h producing complex 1,8-Me2-2,2-(cod)-11-SMe2-2,1,8-closo-RhC2B9H8 (2). Reaction of complex 2 with 1 equiv of I2 in benzene results in a loss of the cod ligand and formation of product 3, consisting of cationic [(1,8-Me2-11-SMe2-closo-2,1,8-RhC2B9H8)2I3]+ (3a+) and anionic [(1,8-Me2-11-SMe-closo-2,1,8-RhC2B9H8)2I3]− (3b–) iodide species. In contrast, unisomerized analog 3,3-(cod)-8-SMe2-closo-3,1,2-RhC2B9H10 reacts with I2 affording dimeric iodide [3,3-I2-8-SMe2-closo-3,1,2-RhC2B9H10]2 (5). The structures of 2 and 5 were determined by a single crystal X-ray diffraction.