Iminoacyl Alkyl Complexes of Zirconium Supported by a Ferrocene-Linked Diphosphinoamide Ligand Scaffold*
Nathan R. Halcovitch A and Michael D. Fryzuk A B
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
B Corresponding author. Email: fryzuk@chem.ubc.ca
Australian Journal of Chemistry 69(5) 555-560 https://doi.org/10.1071/CH15763
Submitted: 8 December 2015 Accepted: 26 January 2016 Published: 16 February 2016
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.
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