Iridium hydride complexes formed by the intramolecular N-H addition of hybrid phosphine amines to iridium(I)

Article abstract of DOI:10.1021/om00141a038

The complexes [MCl(1,5-COD)]₂ react with o-Ph₂PC₆H₄NHR to give tetracoordinated complexes MCl(1,5-COD)(o-Ph₂PC₆H₄NHR) (M = Rh, Ir, R = CH₂Ph; M = Rh, R = Et) where the amine moiety is uncoordinated. Treating IrCl(1,5-COD)(o-Ph₂PC₆H₄NHR) with AgClO₄ gives the bis-chelate complexes [Ir(1,5-COD)(o-Ph₂PC₆H₄NHR)]ClO₄ (R = CH₂Ph, Et). Thermolysis of [Ir(1,5-COD)(o-Ph₂PC₆H₄NHCH ₂Ph)]ClO₄ causes C-cyclometalation to give [IrH(1,5-COD)(o-Ph₂PC₆H₄NHCH₂C ₆H₄)]ClO₄. Treating [Ir(1,5-COD)(o-Ph₂PC₆H₄NHEt)]ClO₄ with L (L = py, MeCN) gives [IrL-(1,5-COD)(o-Ph₂PC₆H₄NHEt)]ClO₄, where the amine is uncoordinated. Cyclooctene in [IrCl(C₈H₁₄)₂]₂ is displaced by o-Ph₂PC₆H₄NHR to give IrHCl(o-Ph₂PC₆H₄NR)(o-Ph₂PC ₆H₄NHR) (R = CH₂Ph, Et). The deuterated analogue o-Ph₂PC₆H₄NDR gives the iridium deuteride complex IrDCl(o-Ph₂PC₆H₄NR)(o-Ph₂PC ₆H₄NDR).