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

Результат исследований: Научные публикации в периодических изданияхстатья

3 Цитирования (Scopus)

Выдержка

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.

Язык оригиналаанглийский
Страницы (с-по)69-74
Число страниц6
ЖурналInorganica Chimica Acta
Том484
DOI
СостояниеОпубликовано - 1 янв 2019

Отпечаток

Cyanamide
cyanamides
Electrospray ionization
Electronic density of states
Methane
Differential thermal analysis
Mass spectrometry
Thermogravimetric analysis
Copper
methane
Ligands
Nuclear magnetic resonance
Single crystals
X ray diffraction
copper
ligands
methylidyne
thermogravimetry
density distribution
cleavage

Предметные области Scopus

  • Физическая и теоретическая химия
  • Неорганическая химия
  • Химия материалов

Цитировать

@article{aab111571d764935bbdde556a9648de8,
title = "Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand",
abstract = "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.",
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",

}

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.

В: Inorganica Chimica Acta, Том 484, 01.01.2019, стр. 69-74.

Результат исследований: Научные публикации в периодических изданияхстатья

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 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 -