Dinuclear complexes of rhodium and iridium with cyanide or thiocyanate bridges: molecular structure of [(PMe2Ph)3Cl2Ir(µ-CN)IrCl2(PMe2Ph)3][ClO4]
- 1 January 1988
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 9,p. 2475-2481
- https://doi.org/10.1039/dt9880002475
Abstract
Reactions of the rhodium or iridium complexes [MCl2(H2O)(PMe2Ph)3][ClO4] with [MCl2(CN)(PMe2Ph)3] give the homometallic cyano-bridged compounds [(PMe2Ph)3Cl2M(CN)M′Cl2(PMe2 Ph)3][ClO4](M = M′= Rh or Ir) and the corresponding heterometallic isomers which do not interconvert. The crystal structure of the complex [(PMe2Ph)3Cl2Ir(CN)IrCl2(PMe2Ph)3][ClO4] revealed that the two IrCl2(PMe2Ph)3 groups are symmetry related because there is a disordered distribution of IrCNIr and IrNClr orientations. Hence, though the structure is well refined (R= 0.035), the different structural influences of the C and N atoms in the bridge could not be defined. However, 13C, 15N, and 31P n.m.r. studies reveal that the trans influence of C is greater than that of the N atom. The corresponding homometallic compounds [(PMe2Ph)3Cl2M(SCN)MCl2(PMe2Ph)3][ClO4](M = Rh or Ir) were obtained but attempted syntheses of the mixed Rh/Ir compounds led to a mixture of all four possible homo- and hetero-metallic species. We conclude that the thiocyanato bridges can cleave to give both S- and N- bonded mononuclear species but N-bonded cyanide monomers are inccessible.Keywords
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