Issue 9, 1986

Bimetallic systems. Part 14. Mixed iridium(I)–platinum(II) acetylide complexes containing bridging Ph2PCH2PPh2 ligands

Abstract

Treatment of the cyclo-octene (C8H14) iridium(I) complex [Ir2Cl2(C8H14)4] with trans-[Pt(C[triple bond, length half m-dash]CR)2(dppm-P)2](R = Ph or p-tolyl; dppm = Ph2PCH2PPh2) gave the dark green complexes [(RC[triple bond, length half m-dash]C)Pt-(µ-dppm)2(µ-C[triple bond, length half m-dash]CR)IrCl], which reacted with dihydrogen to give the dihydrides [(RC[triple bond, length half m-dash]C)2Pt(µ-dppm)2(µ-H)IrH(Cl)]. [(PhC[triple bond, length half m-dash]C)Pt(µ-dppm)2(µ-C[triple bond, length half m-dash]CPh)IrCl] reacted with CO to give [(PhC[triple bond, length half m-dash]C)Pt-(µ-dppm)2(µ-C[triple bond, length half m-dash]CPh)Ir(CO)Cl], more conveniently prepared by treating trans-[IrCl(CO)(PPh3)2] with trans-[Pt(C[triple bond, length half m-dash]CPh)2(dppm-P)2]. The p-tolylacetylide and methylacetylide analogues were prepared similarly. Treatment of [(RC[triple bond, length half m-dash]C)Pt(µ-dppm)2(µ-C[triple bond, length half m-dash]CR)Ir(CO)Cl] with large anions, e.g. PF6 or BPh4, gave the corresponding red cationic species [(RC[triple bond, length half m-dash]C)Pt(µ-dppm)(µ-C[triple bond, length half m-dash]CR)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 [(RC[triple bond, length half m-dash]C)Pt(µ-dppm)2(µ-C[triple bond, length half m-dash]CR)(µ-H)IrH(CO)]+. I.r. and 1H, 31P, and 195Pt n.m.r. data are given.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1986, 1809-1814

Bimetallic systems. Part 14. Mixed iridium(I)–platinum(II) acetylide complexes containing bridging Ph2PCH2PPh2 ligands

D. M. McEwan, D. P. Markham, P. G. Pringle and B. L. Shaw, J. Chem. Soc., Dalton Trans., 1986, 1809 DOI: 10.1039/DT9860001809

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