Reactions of five-co-ordinate iridium(III) hydrides of type [IrHCl2(PBut2R)2](R = Me, Et, or Prn) with π- or σ-bonding ligands and with dihydrogen
- 1 January 1972
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 19,p. 2108-2112
- https://doi.org/10.1039/dt9720002108
Abstract
Five-co-ordinate complexes of type [IrHCl2(PBut 2R)2](R = Me, Et, or Prn) readily take up CO or MeNC(Q) to give six-co-ordinate complexes, [IrHCl2Q(PBut 2R)2] where Q = less bulky tertiary phosphine. [IrHCl2(PBut 2Me)2] will also take up pyridine, 4-methylpyridine, or P(OMe)3 to give adducts [IrHCl2(PBut 2Me)2Q] but with [IrHCl2(PBut 2R)2](R = Et or Prn) these ligands displace a PBut 2R ligand to give [IrHCl2Q2(PBut 2R)]. We have studied the relative affinities of NH3, P(OMe)3, pyridine, 2-methylpyridine, 2,6-dimethylpyridine, dimethyl sulphide, or diethylamine for [IrHCl2(PBut 2Et)2] spectrophotometrically: the first three have strong affinity, the last three very little affinity, and 2-methylpyridine intermediate affinity. [IrHCl2(PBut 2Prn)2], in the presence of sodium isopropoxide takes up dihydrogen to give [IrH5(PBut 2Prn)2] which in turn reacts with carbon monoxide to give [IrH3(CO)(PBut 2Prn)2]. I.r. and 1H and 31P n.m.r. data are given and discussed.Keywords
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