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RESEARCH ARTICLE
Contents Vol 69(5)

CCC-NHC Pincer Zr Diamido Complexes: Synthesis, Characterisation, and Catalytic Activity in Hydroamination/Cyclisation of Unactivated Amino-Alkenes, -Alkynes, and Allenes*

Henry U. Valle A C , Gopalakrishna Akurathi A C , Joon Cho B , Wesley D. Clark A , Amarraj Chakraborty A and T. Keith Hollis A B D
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA.

B Department of Chemistry and Biochemistry, The University of Mississippi, Mississippi State, MS 38677, USA.

C These authors contributed equally to this manuscript.

D Corresponding author. Email: khollis@chemistry.msstate.edu

Australian Journal of Chemistry 69(5) 565-572 https://doi.org/10.1071/CH15795
Submitted: 18 December 2015  Accepted: 21 March 2016   Published: 14 April 2016

Abstract

2-(1,3-Bis-3′-butylimidazol-1′-yl-2′-ylidene)phenylene)bis(dimethylamido) iodo zirconium(iv) (3) and 2-(1,3-bis-3′-butylimidazol-1′-yl-2′-ylidene)phenylene)bis (dimethylamido) bromo zirconium(iv) (4), have been prepared via a modification of the solvent and stoichiometry from the previously reported methodology. The reactivity of 3 and 4 in hydroamination/cyclisation is reported. Both diamido complexes have been found to improve catalytic activity as compared with the previously reported mono-amido analogues. Complexes 3 and 4 were observed to be selective for primary amines over secondary amines in hydroamination/cyclisation. The lack of reactivity with secondary amines is consistent with a mechanism involving requisite formation of a Zr-imido intermediate.


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