Synthesis and characterisation of six Fe(II or III), Co(II) or Zr(IV) complexes containing the ligand [CH(SiMe2R)P(Ph)2NSiMe3]− (R = Me, NEt2) and of [Co{N(SiMe3)C(Ph)C(H)P(Ph)2NSiMe3}2]

The C,N-(trimethylsilyliminodiphenylphosphoranyl)silylmethylmetal complexes [Fe(L)2] (3), [Co(L)2] (4), [ZrCl3(L)]·0.83CH2Cl2 (5), [Fe(L)3] (6), [Fe(L′)2] (7) and [Co(L′)2] (8) have been prepared from the lithium compound Li[CH(SiMe2R)P(Ph)2NSiMe3] [1a, (R = Me) {≡ Li(L)}; 1b, (R = NEt2) {≡ Li(L′)}] and the appropriate metal chloride (or for 7, FeCl3). From Li[N(SiMe3)C(Ph)C(H)P(Ph)2NSiMe3] [≡ Li(L″)] (2), prepared in situ from Li(L) (1a) and PhCN, and CoCl2 there was obtained bis(3-trimethylsilylimino- diphenylphosphoranyl-2-phenyl-N-trimethylsilyl-1-azaallyl-N,N′)cobalt(II) (9). These crystalline complexes 3–9 were characterised by their mass spectra, microanalyses, high spin magnetic moments (not 5) and for 5 multinuclear NMR solution spectra. The X-ray structure of 3 showed it to be a pseudotetrahedral bis(chelate), the iron atom at the spiro junction.

The iminophosphoranylmethyl complexes Fe(L)2, Co(L)2, ZrCl3(L), Fe(L)3, Fe(L)2, Co(L)2 and the iminophosphoranyl-1-azaallyl compound Co{N(SiMe3)C(Ph)C(H)P(Ph)2NSiMe3}2 are reported; [CH(SiMe2R)P(Ph)2NSiMe3] L (R = Me), L′ (R = NEt2).Figure optionsDownload as PowerPoint slide