Abstract

The reactions of 1,1‘-bis(diphenylphosphino)ferrocene (dppf) with a variety of boranes, thiaboranes, and carboranes were found to produce a series of acid−base adducts or, in one case, a phosphonium salt. As confirmed by a single-crystal X-ray study, dppf reacted with BH3·THF or nido-B5H9 to produce the complex dppf(BH3)2 (1) in which the two borane groups are coordinated directly to the phosphorus atoms of the dppf. Depending upon reaction stoichiometries, the reaction of dppf with nido-6-SB9H11 yielded arachno-9-(arachno-9‘-dppf-6‘-SB9H11)-6-SB9H11 (2) or arachno-9-dppf-6-SB9H11 (3). Further reaction of 3 with BH3·THF formed arachno-9-dppf(BH3)-6-SB9H11 (4). The reaction of nido-8-Me2S-7-CB10H12 with dppf produced nido-8-dppf-7-CB10H12 (5), but the analogous reaction with nido-9-Me2S-7,8-C2B9H11 resulted in methyl transfer to dppf to produce the phosphonium salt [dppf-Me+][nido-9-MeS-7,8-C2B9H11-] (6). Reactions of dppf with B10H14 produced both arachno-6,9-(dppf)2B10H12 (7) and oligomeric [arachno-6,9-...

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