Bimetallic systems. Part 15. Some reactions of platinum–manganese carbonyl complexes containing bridging Ph2PCH2PPh2(dppm) ligands

Abstract

Treatment of [(OC)₃Mn(µ-dppm)₂PtCl] with either Li(CCPh) or with PhCCH–NEt₃ gives [(OC)₂Mn(µ-dppm)₂(µ-CO)Pt(CCPh)](1c), in which one of the CO ligands is probably weakly semi-bridging. A CCC₆H₄Me-p complex was made similarly. Treatment of compound (1c) with HBF₄·Et₂O gives [(OC)₃Mn(µ-H)(µ-dppm)₂Pt(CCPh)]BF₄, reversibly. Treatment of [(OC)₃Mn-(µ-dppm)₂PtBr] with NaBH₄ or N₂H₄·H₂O gives the corresponding hydride [(OC)₂Mn(µ-dppm)₂-(µ-CO)PtH] which reacts reversibly with HBF₄·Et₂O to give [(OC)₃Mn(µ-H)(µ-dppm)₂PtH]BF₄. Treatment of [(OC)₃Mn(µ-dppm)₂PtBr] with TIPF₆–CO gives [(OC)₃Mn(µ-dppm)₂Pt(CO)]PF₆, which is protonated by HBF₄·Et₂O to give [(OC)₃Mn(µ-H)(µ-dppm)₂Pt(CO)]BF₄(PF₆) and also reacts reversibly with OMe^– to give [(OC)₂Mn(µ-dppm)₂(µ-CO)Pt(CO₂Me)]. The compound [(OC)₃Mn(µ-dppm)₂PtBr] reacts with CNBu^t to give [(OC)₂Mn(µ-dppm)₂(µ-CO)Pt(CNBu^t)]⁺ which, in turn, could be protonated reversibly by HBF₄·Et₂O to give [(OC)₃Mn(µ-H)(µ-dppm)₂-Pt(CNBu^t)]²⁺, isolated as the mixed BF₄^––PF₆^– salt. Treatment of [(OC)₃Mn(µ-dppm)₂PtBr] with NOBF₄ gives an NO⁺ adduct possibly with a weakly bridging NO ligand, viz. [(OC)₃Mn(µ-dppm)₂(µ-NO)PtBr]BF₄. Hydrogen-1, ³¹P-{¹H} n.m.r, and i.r. data are given.