Abstract
The complexes [Cu{HC(3,5-Me(2)pz)(3)}(NCNR2)1[BF4] (1-8; R-2 = Me-2 1, Et-2 2, C5H10 3, C4H8O 4, C4H8 5, C3H6C6H4 [NC3H6C6H4 is 1,2,3,4-dihydroisoquinoline-2-yl] 6, (CH2Ph)(2) 7, (Me)Ph 8) were prepared by the reaction of [Cu(NCMe)(4)] [BF4] with HC(3,5-Me(2)pz)(3) and NCNR2 (CH2Cl2, 20-25 degrees C) and these species were characterized by C, H, N analyses, high resolution mass-spectrometry with electrospray ionization, H-1, C-13{H-1} 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(2)pz)(3)}(NCNMe2)](+), [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+), and [Cu{HC(3,5-Me(2)pz)(3)}(CNMe)](+) model species. The nature of Cu-N coordination bonds in [Cu{ HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) and [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+) is very similar, whereas Cu-C contact in [Cu({HC(3,5-Me(2)pz)(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(2)pz)(3)}(NCMe)](+) (36 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) (41 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(3)}(CNMe)](+) (47 kcal/mol), and these theoretical data are coherent with the experimental observations.
| Original language | English |
|---|---|
| Pages (from-to) | 69-74 |
| Number of pages | 6 |
| Journal | Inorganica Chimica Acta |
| Volume | 484 |
| DOIs | |
| Publication status | Published - 1 Jan 2019 |
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Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry
Cite this
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Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand. / Бокач, Надежда Арсеньевна; Мелехова, Анна Андреевна; Новиков, Александр Сергеевич; Дубовцев, Алексей Юрьевич; Золотарев, Андрей Анатольевич.
In: Inorganica Chimica Acta, Vol. 484, 01.01.2019, p. 69-74.Research output
TY - JOUR
T1 - Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand
AU - Бокач, Надежда Арсеньевна
AU - Мелехова, Анна Андреевна
AU - Новиков, Александр Сергеевич
AU - Дубовцев, Алексей Юрьевич
AU - Золотарев, Андрей Анатольевич
PY - 2019/1/1
Y1 - 2019/1/1
N2 - The complexes [Cu{HC(3,5-Me(2)pz)(3)}(NCNR2)1[BF4] (1-8; R-2 = Me-2 1, Et-2 2, C5H10 3, C4H8O 4, C4H8 5, C3H6C6H4 [NC3H6C6H4 is 1,2,3,4-dihydroisoquinoline-2-yl] 6, (CH2Ph)(2) 7, (Me)Ph 8) were prepared by the reaction of [Cu(NCMe)(4)] [BF4] with HC(3,5-Me(2)pz)(3) and NCNR2 (CH2Cl2, 20-25 degrees C) and these species were characterized by C, H, N analyses, high resolution mass-spectrometry with electrospray ionization, H-1, C-13{H-1} 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(2)pz)(3)}(NCNMe2)](+), [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+), and [Cu{HC(3,5-Me(2)pz)(3)}(CNMe)](+) model species. The nature of Cu-N coordination bonds in [Cu{ HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) and [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+) is very similar, whereas Cu-C contact in [Cu({HC(3,5-Me(2)pz)(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(2)pz)(3)}(NCMe)](+) (36 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) (41 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(3)}(CNMe)](+) (47 kcal/mol), and these theoretical data are coherent with the experimental observations.
AB - The complexes [Cu{HC(3,5-Me(2)pz)(3)}(NCNR2)1[BF4] (1-8; R-2 = Me-2 1, Et-2 2, C5H10 3, C4H8O 4, C4H8 5, C3H6C6H4 [NC3H6C6H4 is 1,2,3,4-dihydroisoquinoline-2-yl] 6, (CH2Ph)(2) 7, (Me)Ph 8) were prepared by the reaction of [Cu(NCMe)(4)] [BF4] with HC(3,5-Me(2)pz)(3) and NCNR2 (CH2Cl2, 20-25 degrees C) and these species were characterized by C, H, N analyses, high resolution mass-spectrometry with electrospray ionization, H-1, C-13{H-1} 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(2)pz)(3)}(NCNMe2)](+), [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+), and [Cu{HC(3,5-Me(2)pz)(3)}(CNMe)](+) model species. The nature of Cu-N coordination bonds in [Cu{ HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) and [Cu{HC(3,5-Me(2)pz)(3)}(NCMe)](+) is very similar, whereas Cu-C contact in [Cu({HC(3,5-Me(2)pz)(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(2)pz)(3)}(NCMe)](+) (36 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(3)}(NCNMe2)](+) (41 kcal/mol) <[Cu{HC(3,5-Me(2)pz)(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 -