Copper(i) complexes: intramolecular and intermolecular arene-c– h···π(quasi-chelate ring) interactions

Yeo, Chien Ing * and Zukerman-Schpector, Julio and Ferreira, M. A. B and Tiekink, Edward R. T. * (2017) Copper(i) complexes: intramolecular and intermolecular arene-c– h···π(quasi-chelate ring) interactions. In: Asian Conference on Coordination Chemistry (6th), 23 - 28 July 2017, Melbourne, Australia. (Submitted)

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Abstract

A series of bis(phosphane)copper(I) thiocarbamates, namely (Ph3P)2Cu[ROC(=S)N(H)Ph]Cl, were prepared in response to the promising biological properties exhibited by the related phosphanegold(I) analogues. The presence of an intramolecular N-H···Cl hydrogen bond in the title compounds, was found leading to the formation of a six-membered quasi-chelate ring, {CuCl···HNCS}. Following ring closure, unanticipated C–H···π(quasi-chelate ring) interactions were evidenced in one-third of related copper(I) complexes capable of forming similar quasi-chelate rings. Computational chemistry calculations revealed that these interactions when occurring intramolecularly, afforded energies of attraction approximating 3.5 kcal mol-1. In a subsequent review of analogous copper(I) complexes, intermolecular C–H…π(quasi-chelate) interactions imparted stabilisation to the crystal structures, leading to zero-, one-, two- and even threedimensional architectures.

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