| Abstract |
The complexes [Cu(tpm*)(CNR)](BF4) (tpm* = tris(3,5-dimethylpyrazolyl)methane; R = Xyl [1](BF4), 2-Cl-6-MeC6H3 [2](BF4), Cy [3](BF4)) were prepared by the reaction of [Cu(NCMe)(4)](BF4) with tpm* and CNR (CH2Cl2, 20-25 degrees C) and these species were characterized by elemental analyses, molar conductivities, high resolution ESI+-MS, IR, H-1 and C-13\H-1\ NMR spectroscopies and also X-ray diffraction for [1](BF4) and [2](BF4). Results of the theoretical DFT (M06/6-31G(d)) study of binding in the copper complexes using NBO and CDA analyses indicate that (i) the influence of crystal packing effects on the geometrical features of [Cu(tpm*)(CNXyl)](+) cation is insignificant, (ii) the coordination bonds Cu-C in the tris-pyrazolyl-methane isocyanide complexes are relatively strong exceeding 50 kcal/mol, and (iii) the CDA data for these systems demonstrate that the \M\ <- L sigma-donation prevails over the \M\-> L pi-back-donation. (C) 2016 Elsevier B.V. All rights reserved. |
