Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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Linear Trinuclear Copper(ii) Complexes Derived from the Nucleophilic Addition Products of Dicyanonitrosomethanide [C(CN)2(NO)]: Syntheses, Structures, and Magnetic Properties*

Mohd. R. Razali A , Aron Urbatsch A , Stuart K. Langley A , Jonathan G. MacLellan A , Glen B. Deacon A , Boujemaa Moubaraki A , Keith. S. Murray A and Stuart R. Batten A B
+ Author Affiliations
- Author Affiliations

A School of Chemistry, Monash University, Vic. 3800, Australia.

B Corresponding author. Email: stuart.batten@monash.edu.au

Australian Journal of Chemistry 65(7) 918-925 https://doi.org/10.1071/CH12100
Submitted: 16 February 2012  Accepted: 9 April 2012   Published: 19 July 2012

Abstract

Two novel trinuclear CuII complexes have been synthesised from the nucleophilic addition derivatives of the small cyano anion, dicyanonitrosomethanide (dcnm). The reaction of CuII with the water adduct ligand, carbamoylcyanonitrosomethanide (ccnm) and teaH3 (triethanolamine) in a basic MeOH/MeCN solution results in the formation of [Cu3(acnm)2(teaH2)2]·2MeOH (1) (acnm = amidocarbonyl(cyano)nitrosomethanide and teaH2 = singly deprotonated triethanolamine). The reaction of CuII with dicyanonitrosomethanide (dcnm) and m-xylenediamine in a basic MeOH/MeCN solution results in the formation of [Cu3(cimm)2(a3acnm)2]·6MeCN (2) (cimm = cyano(imido(methoxy)methyl)nitrosomethanide and a3acnm = {amino(3-aminomethylphenyl)methylimino}methyl(cyanonitrosomethanide)). Both complexes display linear trinuclear CuII metallic cores. Solid state DC magnetic susceptibility studies were performed on 1 and 2. Compound 1 revealed very strong antiferromagnetic interactions between central and terminal Cu atoms, while compound 2 displayed ferromagnetic interactions because of the orthogonal relationship of the terminal CH12100_IE1.gif and the central CH12100_IE2.gif ‘magnetic’ orbitals, which contrasts with these orbitals being coplanar in 1 thus providing strong superexchange pathways involving Cu-N-O-Cu moieties.


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