Structural characterization of a tetrametallic diamine-bis(phenolate) complex of lithium and synthesis of a related bismuth complex

Kerton, Francesca M. and Drover, Marcus W. and Murphy, Jennifer N. and Flogeras, Jenna C. and Schneider, Celine M. and Dawe, Louise N. (2015) Structural characterization of a tetrametallic diamine-bis(phenolate) complex of lithium and synthesis of a related bismuth complex. Polyhedron, 102. pp. 60-68. ISSN 1873-3719

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Abstract

A novel lithium complex was prepared from the reaction of 1,4-bis(2-hydroxy-3,5-di-tert-butyl-benzyl)imidazolidine H2[O2N2]BuBuIm (L1H2) with n-butyllithium to provide the corresponding tetralithium amine-bis(phenolate) complex {Li2[L1]}2·4THF, 1. Variable temperature 7Li NMR revealed that this complex is labile in solution, dissociating at elevated temperatures to afford two dilithium entities. Additionally, 7Li MAS NMR was performed on 1 to provide information regarding the lithium coordination environment in the bulk solid-state. The reactivity of 1 was assessed in the ring-expansion polymerization of ε-caprolactone (ε-CL), which was first order in ε-CL with an activation energy of 50.9 kJmol−1. Reaction of 1 and a related Li complex (formed in situ) with BiCl3 afforded hydrolytically unstable bismuth phenolate species, as evidenced by the isolation and structural characterization of [Bi4(Cl)3(μ-Cl)(μ-O)(O)2{[O2N2]BuBuPip}2], 2, where [O2N2]BuBuPip is the homopiperazine-containing analog of L1.

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