The complexes [Cu{HC(3,5-Me 2pz) 3}(NCNR 2)][BF 4] (1–8; R 2 = Me 2 1, Et 2 2, C 5H 10 3, C 4H 8O 4, C 4H 8 5, C 3H 6C 6H 4 [NC 3H 6C 6H 4 is 1,2,3,4-dihydroisoquinoline-2-yl] 6, (CH 2Ph) 2 7, (Me)Ph 8) were prepared by the reaction of [Cu(NCMe) 4][BF 4] with HC(3,5-Me 2pz) 3 and NCNR 2 (CH 2Cl 2, 20–25 °C) and these species were characterized by C, H, N analyses, high resolution mass-spectrometry with electrospray ionization, 1H, 13C{ 1H} NMR and FTIR spectroscopic techniques, molar conductivity measurements, thermogravimetry/differential thermal analysis, and also by single-crystal X-ray diffraction for 3. The theoretical topological analysis of the electron density distribution (QTAIM method) together with the NBO analysis were applied to study the nature of Cu–N and Cu–C coordination bonds in [Cu{HC(3,5-Me 2pz) 3}(NCNMe 2)] +, [Cu{HC(3,5-Me 2pz) 3}(NCMe)] +, and [Cu{HC(3,5-Me 2pz) 3}(CNMe)] + model species. The nature of Cu–N coordination bonds in [Cu{HC(3,5-Me 2pz) 3}(NCNMe 2)] + and [Cu{HC(3,5-Me 2pz) 3}(NCMe)] + is very similar, whereas Cu–C contact in [Cu({HC(3,5-Me 2pz) 3}(CNMe)] + is relatively more covalent. The calculated vertical total energies for the Cu–N and Cu–C coordination bonds cleavage increase in the following row: [Cu{HC(3,5-Me 2pz) 3}(NCMe)] + (36 kcal/mol) < [Cu{HC(3,5-Me 2pz) 3}(NCNMe 2)] + (41 kcal/mol) < [Cu{HC(3,5-Me 2pz) 3}(CNMe)] + (47 kcal/mol), and these theoretical data are coherent with the experimental observations.

Original languageEnglish
Pages (from-to)69-74
Number of pages6
JournalInorganica Chimica Acta
Publication statusPublished - 1 Jan 2019


Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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