Bimetallic systems. Part 14. Mixed iridium(I)–platinum(II) acetylide complexes containing bridging Ph2PCH2PPh2ligands

Abstract
Treatment of the cyclo-octene (C8H14) iridium(I) complex [Ir2Cl2(C8H14)4] with trans-[Pt(CCR)2(dppm-P)2](R = Ph or p-tolyl; dppm = Ph2PCH2PPh2) gave the dark green complexes [(RCC)Pt-(µ-dppm)2(µ-CCR)IrCl], which reacted with dihydrogen to give the dihydrides [(RCC)2Pt(µ-dppm)2(µ-H)IrH(Cl)]. [(PhCC)Pt(µ-dppm)2(µ-CCPh)IrCl] reacted with CO to give [(PhCC)Pt-(µ-dppm)2(µ-CCPh)Ir(CO)Cl], more conveniently prepared by treating trans-[IrCl(CO)(PPh3)2] with trans-[Pt(CCPh)2(dppm-P)2]. The p-tolylacetylide and methylacetylide analogues were prepared similarly. Treatment of [(RCC)Pt(µ-dppm)2(µ-CCR)Ir(CO)Cl] with large anions, e.g. PF6 or BPh4 , gave the corresponding red cationic species [(RCC)Pt(µ-dppm)(µ-CCR)Ir-(CO)]+, isolated as PF6 or BPh4 salts. The conversion was reversed by addition of Cl. These cations (R = Me, Ph, or p-tolyl) reacted rapidly with dihydrogen to give the corresponding dihydrides [(RCC)Pt(µ-dppm)2(µ-CCR)(µ-H)IrH(CO)]+. I.r. and 1H, 31P, and 195Pt n.m.r. data are given.

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