Iminoacyl Alkyl Complexes of Zirconium Supported by a Ferrocene-Linked Diphosphinoamide Ligand Scaffold

Abstract

Zirconium dialkyl complexes of the general formula fc(NPiPr2)2ZrR2 (where fc = 1,1′-ferrocenyl, R = CH3, CH2Ph, CH2tBu, tBu) have been synthesized and characterized via the addition of alkyl lithium or potassium benzyl derivatives to the dichloride complex fc(NPiPr2)2ZrCl2(THF). Addition of 2,6-dimethylphenylisocyanide to these alkyl derivatives generates the corresponding mono iminoacyl alkyl zirconium complexes. On thermolysis, the iminoacyl moiety containing a benzyl substituent undergoes rearrangement to yield a new complex that contains an alkene-amido fragment. Mechanistic studies point to a 1,2 hydrogen shift as the rate-determining step.