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 -