Journal
JOURNAL OF CHEMICAL RESEARCH
Volume -, Issue 1, Pages 1-4Publisher
SAGE PUBLICATIONS LTD
DOI: 10.3184/174751912X13246611263215
Keywords
copper(II); crystal structure; semicoordination; redox; ligand substitution; density functional theory
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Funding
- DST under FIST
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The complex [CuL2(OClO3)(2)] [L=2-(benzylthio)aniline] has been synthesised and its crystal structure determined. It displays a one-electron reductive response at -0.38 V versus SCE and its reactions with N-3(-) and SCN- ions give [CuL2(N-3)(2)] and [CuL2(SCN)(2)]. The copper atom in [CuL2(OClO3)(2)] assumes a tetragonally distorted, octahedral geometry with two semicoordinated perchlorate oxygens in the axial positions. Two perchlorate ions are also linked to the amino nitrogen of other molecules by intermolecular hydrogen bonding. A plausible description of redox orbitals is given on the basis of single point density functional theory calculations.
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