Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Experimental and Computational Studies of the Mechanisms of Hydroamination/Cyclisation of Unactivated α,ω-Amino-alkenes with CCC-NHC Pincer Zr Complexes*

Wesley D. Clark A B , Katherine N. Leigh C , Charles Edwin Webster A C D 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, Oxford, MS 38655, USA.

C Department of Chemistry, The University of Memphis, Memphis, TN 38152, USA.

D Corresponding authors. Email: ewebster@chemistry.msstate.edu; khollis@chemistry.msstate.edu

Australian Journal of Chemistry 69(5) 573-582 https://doi.org/10.1071/CH15779
Submitted: 12 December 2015  Accepted: 7 March 2016   Published: 11 April 2016

Abstract

Four new CCC-NHC pincer Zr complexes have been synthesised, characterised, and used in mechanistic studies in the hydroamination/cyclisation of unactivated amino-alkenes. These Zr pre-catalysts will cyclise a primary amino-alkene, but no reaction was observed for a secondary amino-alkene even in the presence of a primary amine. The empirical rate law, experimentally determined activation parameters, and kinetic isotope effects (KIEs) are reported. Several possible mechanisms, including amido- versus imido-insertion and concerted-insertion versus [2 + 2] cycloaddition mechanisms, were modelled computationally at the PBEPBE level of theory with double-zeta quality basis sets. The formation of a catalytically relevant imido complex via the monoamido complexes was accompanied by in situ formation of ammonium salts of the substrates. The experimental and computational data are consistent with an imido-[2 + 2] cycloaddition mechanism for the CCC-NHC pincer diamido Zr complexes that follow saturation kinetics under catalytically relevant concentrations.


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