Imidotungsten(vi) complexes with chelating amino and imino phenolates

Abstract

The reaction of WOCl₄ with 2,4-di-tert-butyl-6-((isopropylamino)methyl)phenol followed by the reaction with phenyl isocyanate leads to the formation of imidotungsten(VI) complex [W(NPh)Cl₃(OC₆H₃(CH₂NH-i-Pr)-2-t-Bu₂-4,6)] 4 with a chelating aminophenolate ligand. When the same procedure was applied using aminophenols with bulkier substituents in the amino group, the final product was an unexpected Schiff-base complex [W(NPh)Cl₃(OC₆H₃(CHNPh)-2-t-Bu₂-4,6)] 5, where the ligand is derived from 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol. Complex 5 is also formed in the thermal degradation of 4. On the whole, 5 appears to be formed by a disproportionation of intermediate compounds, which are analogous to complex 4. The solid-state structures of 4 and 5 have been determined by X-ray crystallography whereas the solution structures were studied by ¹H and ¹³C NMR.