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

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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.

LanguageEnglish
Pages69-74
Number of pages6
JournalInorganica Chimica Acta
Volume484
DOIs
StatePublished - 1 Jan 2019

Keywords

  • Copper(I)
  • Dialkylcyanamide ligands
  • NBO analysis
  • QTAIM method
  • Tris-pyrazolylmethane complexes
  • X-RAY-STRUCTURE
  • REACTIVITY
  • DIALKYLCYANAMIDES
  • CYCLOADDITION
  • CYANOGUANIDINE COMPLEXES
  • TRIS(PYRAZOLYL)METHANE
  • GENERATION
  • DERIVATIVES
  • METAL-COMPLEXES
  • ORGANOCYANAMIDE

Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{aab111571d764935bbdde556a9648de8,
title = "Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand",
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.",
keywords = "Copper(I), Dialkylcyanamide ligands, NBO analysis, QTAIM method, Tris-pyrazolylmethane complexes, X-RAY-STRUCTURE, REACTIVITY, DIALKYLCYANAMIDES, CYCLOADDITION, CYANOGUANIDINE COMPLEXES, TRIS(PYRAZOLYL)METHANE, GENERATION, DERIVATIVES, METAL-COMPLEXES, ORGANOCYANAMIDE",
author = "Бокач, {Надежда Арсеньевна} and Мелехова, {Анна Андреевна} and Новиков, {Александр Сергеевич} and Дубовцев, {Алексей Юрьевич} and Золотарев, {Андрей Анатольевич}",
year = "2019",
month = "1",
day = "1",
doi = "10.1016/j.ica.2018.09.024",
language = "English",
volume = "484",
pages = "69--74",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier",

}

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

T2 - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -