TY - JOUR

T1 - Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand

AU - Melekhova, A. A.

AU - Novikov, Alexander S.

AU - Dubovtsev, Alexey Yu.

AU - Zolotarev, Andrey A.

AU - Bokach, Nadezhda A.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

KW - Copper(I)

KW - Dialkylcyanamide ligands

KW - NBO analysis

KW - QTAIM method

KW - Tris-pyrazolylmethane complexes

KW - X-RAY-STRUCTURE

KW - REACTIVITY

KW - DIALKYLCYANAMIDES

KW - CYCLOADDITION

KW - CYANOGUANIDINE COMPLEXES

KW - TRIS(PYRAZOLYL)METHANE

KW - GENERATION

KW - DERIVATIVES

KW - METAL-COMPLEXES

KW - ORGANOCYANAMIDE

UR - http://www.scopus.com/inward/record.url?scp=85053419958&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2018.09.024

DO - 10.1016/j.ica.2018.09.024

M3 - Article

VL - 484

SP - 69

EP - 74

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -