X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes

Constantinus F. Martens, Albertus P.H.J. Schenning, Martinus C. Feiters, Harry W. Berens, Johannes G.M. van der Linden, Gert Admiraal, Paul T. Beurskens, Huub Kooijman, Anthony L. Spek, Roeland J.M. Nolte

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Abstract

The copper complexes of bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl]amine (1) and its benzylated derivative (2) have been studied as single crystals by X-ray crystallography and as powders and solutions by a variety of techniques. [Cu(1)·2NO3] (C14H25CUN7O7 including 1 H2O, 3) crystallized in the monoclinic space group Pc (No. 7) with a = 8.1596(9) Å,b = 31.164(2) Å, c = 7.7966(9) Å, β = 94.75(2)°, V = 1975.7(3) Å3, and Z = 4 (structure refinement converged to RF = 0.066 and RwF2 = 0.227); [Cu(1)C1O4·C2H5OH]C1O4 (C16H29CI2CUN5O9, 4) crystallized in the orthorhombic space group Pna21 (No. 33) with a = 13.3463(7) Å, b = 10.3925(9) Å, c = 17.511(1) Å, V = 2432.1(3) Å3, and Z = 4 (refined to RF = 0.063 and RwF = 0.052); [Cu(2)·2NO3] (C21H29-CuN7O6, 5) crystallized in the monoclinic space group C2/c (No.15) with a = 28.719(2) Å, b = 8.6043(6) Å, c = 23.034(2) Å, β = 124.767(7)°, V = 4675.7(7) Å3, and Z = 8 (refined to RF = 0.042 and RwF = 0.034); [Cu·(2)·C2H5OH·Y](C1O4)″ (C48H78Cl4Cu2N10O20, 6) (Y = H2O, n = 2, or C1O4, n = 1) crystallized in the monoclinic space group P21/c (No. 14) with a = 10.9488(9) Å,b = 17.030(2) Å, c = 32.893(3) Å, β = 92.185-(7)°, V= 6129(1) Å3, and Z = 4 (refined to RF = 0.104 and RwF = 0.119). In complexes 3, 4, and 6, the ligand coordinated Cu(II) with a T-shaped arrangement of the nitrogen donor atoms. Ethanol coordinated in one of the apical positions in complexes 4 and 6. The amine nitrogen moved from the basal plane in 3 to the apical position in 5, where the copper had square pyramidal coordination geometry. The largest difference between 4 and 6 was a lengthening of 0.1 Å in the bond between the Cu(II) and the amine nitrogen. Conductivity measurements revealed that the nitrate complexes behave as 1:1 electrolytes in acetonitrile solution, whereas the Perchlorate complexes behaved as 2:1 electrolytes. The half-wave potentials, measured in acetonitrile by cyclic voltammetry, were −0.01, +0.15, +0.10, and +0.28 V for 3–6, respectively. The high redox potentials of the copper(II) bis(pyrazole) complexes, in particular for complex 6, are explained by the fact that the Cu(II) complexes have the correct ligand geometry for the stabilization of Cu(I).

LanguageEnglish
Pages4735-4744
Number of pages10
JournalInorganic Chemistry
Volume34
Issue number19
DOIs
StatePublished - 1 Sep 1995

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Amines
Copper
Nitrogen
X rays
copper
amines
Electrolytes
nitrogen
Ligands
acetonitrile
x rays
Geometry
X ray crystallography
electrolytes
Nitrates
Powders
ligands
Cyclic voltammetry
Ethanol
Stabilization

Cite this

Martens, C. F., Schenning, A. P. H. J., Feiters, M. C., Berens, H. W., van der Linden, J. G. M., Admiraal, G., ... Nolte, R. J. M. (1995). X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes. Inorganic Chemistry, 34(19), 4735-4744. DOI: 10.1021/ic00123a005
Martens, Constantinus F. ; Schenning, Albertus P.H.J. ; Feiters, Martinus C. ; Berens, Harry W. ; van der Linden, Johannes G.M. ; Admiraal, Gert ; Beurskens, Paul T. ; Kooijman, Huub ; Spek, Anthony L. ; Nolte, Roeland J.M./ X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes. In: Inorganic Chemistry. 1995 ; Vol. 34, No. 19. pp. 4735-4744
@article{40119a52505347f0a45fd0bfb625fc20,
title = "X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes",
abstract = "The copper complexes of bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl]amine (1) and its benzylated derivative (2) have been studied as single crystals by X-ray crystallography and as powders and solutions by a variety of techniques. [Cu(1)·2NO3] (C14H25CUN7O7 including 1 H2O, 3) crystallized in the monoclinic space group Pc (No. 7) with a = 8.1596(9) {\AA},b = 31.164(2) {\AA}, c = 7.7966(9) {\AA}, β = 94.75(2)°, V = 1975.7(3) {\AA}3, and Z = 4 (structure refinement converged to RF = 0.066 and RwF2 = 0.227); [Cu(1)C1O4·C2H5OH]C1O4 (C16H29CI2CUN5O9, 4) crystallized in the orthorhombic space group Pna21 (No. 33) with a = 13.3463(7) {\AA}, b = 10.3925(9) {\AA}, c = 17.511(1) {\AA}, V = 2432.1(3) {\AA}3, and Z = 4 (refined to RF = 0.063 and RwF = 0.052); [Cu(2)·2NO3] (C21H29-CuN7O6, 5) crystallized in the monoclinic space group C2/c (No.15) with a = 28.719(2) {\AA}, b = 8.6043(6) {\AA}, c = 23.034(2) {\AA}, β = 124.767(7)°, V = 4675.7(7) {\AA}3, and Z = 8 (refined to RF = 0.042 and RwF = 0.034); [Cu·(2)·C2H5OH·Y](C1O4)″ (C48H78Cl4Cu2N10O20, 6) (Y = H2O, n = 2, or C1O4−, n = 1) crystallized in the monoclinic space group P21/c (No. 14) with a = 10.9488(9) {\AA},b = 17.030(2) {\AA}, c = 32.893(3) {\AA}, β = 92.185-(7)°, V= 6129(1) {\AA}3, and Z = 4 (refined to RF = 0.104 and RwF = 0.119). In complexes 3, 4, and 6, the ligand coordinated Cu(II) with a T-shaped arrangement of the nitrogen donor atoms. Ethanol coordinated in one of the apical positions in complexes 4 and 6. The amine nitrogen moved from the basal plane in 3 to the apical position in 5, where the copper had square pyramidal coordination geometry. The largest difference between 4 and 6 was a lengthening of 0.1 {\AA} in the bond between the Cu(II) and the amine nitrogen. Conductivity measurements revealed that the nitrate complexes behave as 1:1 electrolytes in acetonitrile solution, whereas the Perchlorate complexes behaved as 2:1 electrolytes. The half-wave potentials, measured in acetonitrile by cyclic voltammetry, were −0.01, +0.15, +0.10, and +0.28 V for 3–6, respectively. The high redox potentials of the copper(II) bis(pyrazole) complexes, in particular for complex 6, are explained by the fact that the Cu(II) complexes have the correct ligand geometry for the stabilization of Cu(I).",
author = "Martens, {Constantinus F.} and Schenning, {Albertus P.H.J.} and Feiters, {Martinus C.} and Berens, {Harry W.} and {van der Linden}, {Johannes G.M.} and Gert Admiraal and Beurskens, {Paul T.} and Huub Kooijman and Spek, {Anthony L.} and Nolte, {Roeland J.M.}",
year = "1995",
month = "9",
day = "1",
doi = "10.1021/ic00123a005",
language = "English",
volume = "34",
pages = "4735--4744",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "19",

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Martens, CF, Schenning, APHJ, Feiters, MC, Berens, HW, van der Linden, JGM, Admiraal, G, Beurskens, PT, Kooijman, H, Spek, AL & Nolte, RJM 1995, 'X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes' Inorganic Chemistry, vol. 34, no. 19, pp. 4735-4744. DOI: 10.1021/ic00123a005

X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes. / Martens, Constantinus F.; Schenning, Albertus P.H.J.; Feiters, Martinus C.; Berens, Harry W.; van der Linden, Johannes G.M.; Admiraal, Gert; Beurskens, Paul T.; Kooijman, Huub; Spek, Anthony L.; Nolte, Roeland J.M.

In: Inorganic Chemistry, Vol. 34, No. 19, 01.09.1995, p. 4735-4744.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes

AU - Martens,Constantinus F.

AU - Schenning,Albertus P.H.J.

AU - Feiters,Martinus C.

AU - Berens,Harry W.

AU - van der Linden,Johannes G.M.

AU - Admiraal,Gert

AU - Beurskens,Paul T.

AU - Kooijman,Huub

AU - Spek,Anthony L.

AU - Nolte,Roeland J.M.

PY - 1995/9/1

Y1 - 1995/9/1

N2 - The copper complexes of bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl]amine (1) and its benzylated derivative (2) have been studied as single crystals by X-ray crystallography and as powders and solutions by a variety of techniques. [Cu(1)·2NO3] (C14H25CUN7O7 including 1 H2O, 3) crystallized in the monoclinic space group Pc (No. 7) with a = 8.1596(9) Å,b = 31.164(2) Å, c = 7.7966(9) Å, β = 94.75(2)°, V = 1975.7(3) Å3, and Z = 4 (structure refinement converged to RF = 0.066 and RwF2 = 0.227); [Cu(1)C1O4·C2H5OH]C1O4 (C16H29CI2CUN5O9, 4) crystallized in the orthorhombic space group Pna21 (No. 33) with a = 13.3463(7) Å, b = 10.3925(9) Å, c = 17.511(1) Å, V = 2432.1(3) Å3, and Z = 4 (refined to RF = 0.063 and RwF = 0.052); [Cu(2)·2NO3] (C21H29-CuN7O6, 5) crystallized in the monoclinic space group C2/c (No.15) with a = 28.719(2) Å, b = 8.6043(6) Å, c = 23.034(2) Å, β = 124.767(7)°, V = 4675.7(7) Å3, and Z = 8 (refined to RF = 0.042 and RwF = 0.034); [Cu·(2)·C2H5OH·Y](C1O4)″ (C48H78Cl4Cu2N10O20, 6) (Y = H2O, n = 2, or C1O4−, n = 1) crystallized in the monoclinic space group P21/c (No. 14) with a = 10.9488(9) Å,b = 17.030(2) Å, c = 32.893(3) Å, β = 92.185-(7)°, V= 6129(1) Å3, and Z = 4 (refined to RF = 0.104 and RwF = 0.119). In complexes 3, 4, and 6, the ligand coordinated Cu(II) with a T-shaped arrangement of the nitrogen donor atoms. Ethanol coordinated in one of the apical positions in complexes 4 and 6. The amine nitrogen moved from the basal plane in 3 to the apical position in 5, where the copper had square pyramidal coordination geometry. The largest difference between 4 and 6 was a lengthening of 0.1 Å in the bond between the Cu(II) and the amine nitrogen. Conductivity measurements revealed that the nitrate complexes behave as 1:1 electrolytes in acetonitrile solution, whereas the Perchlorate complexes behaved as 2:1 electrolytes. The half-wave potentials, measured in acetonitrile by cyclic voltammetry, were −0.01, +0.15, +0.10, and +0.28 V for 3–6, respectively. The high redox potentials of the copper(II) bis(pyrazole) complexes, in particular for complex 6, are explained by the fact that the Cu(II) complexes have the correct ligand geometry for the stabilization of Cu(I).

AB - The copper complexes of bis[2-(3,5-dimethyl-l-pyrazolyl)ethyl]amine (1) and its benzylated derivative (2) have been studied as single crystals by X-ray crystallography and as powders and solutions by a variety of techniques. [Cu(1)·2NO3] (C14H25CUN7O7 including 1 H2O, 3) crystallized in the monoclinic space group Pc (No. 7) with a = 8.1596(9) Å,b = 31.164(2) Å, c = 7.7966(9) Å, β = 94.75(2)°, V = 1975.7(3) Å3, and Z = 4 (structure refinement converged to RF = 0.066 and RwF2 = 0.227); [Cu(1)C1O4·C2H5OH]C1O4 (C16H29CI2CUN5O9, 4) crystallized in the orthorhombic space group Pna21 (No. 33) with a = 13.3463(7) Å, b = 10.3925(9) Å, c = 17.511(1) Å, V = 2432.1(3) Å3, and Z = 4 (refined to RF = 0.063 and RwF = 0.052); [Cu(2)·2NO3] (C21H29-CuN7O6, 5) crystallized in the monoclinic space group C2/c (No.15) with a = 28.719(2) Å, b = 8.6043(6) Å, c = 23.034(2) Å, β = 124.767(7)°, V = 4675.7(7) Å3, and Z = 8 (refined to RF = 0.042 and RwF = 0.034); [Cu·(2)·C2H5OH·Y](C1O4)″ (C48H78Cl4Cu2N10O20, 6) (Y = H2O, n = 2, or C1O4−, n = 1) crystallized in the monoclinic space group P21/c (No. 14) with a = 10.9488(9) Å,b = 17.030(2) Å, c = 32.893(3) Å, β = 92.185-(7)°, V= 6129(1) Å3, and Z = 4 (refined to RF = 0.104 and RwF = 0.119). In complexes 3, 4, and 6, the ligand coordinated Cu(II) with a T-shaped arrangement of the nitrogen donor atoms. Ethanol coordinated in one of the apical positions in complexes 4 and 6. The amine nitrogen moved from the basal plane in 3 to the apical position in 5, where the copper had square pyramidal coordination geometry. The largest difference between 4 and 6 was a lengthening of 0.1 Å in the bond between the Cu(II) and the amine nitrogen. Conductivity measurements revealed that the nitrate complexes behave as 1:1 electrolytes in acetonitrile solution, whereas the Perchlorate complexes behaved as 2:1 electrolytes. The half-wave potentials, measured in acetonitrile by cyclic voltammetry, were −0.01, +0.15, +0.10, and +0.28 V for 3–6, respectively. The high redox potentials of the copper(II) bis(pyrazole) complexes, in particular for complex 6, are explained by the fact that the Cu(II) complexes have the correct ligand geometry for the stabilization of Cu(I).

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U2 - 10.1021/ic00123a005

DO - 10.1021/ic00123a005

M3 - Article

VL - 34

SP - 4735

EP - 4744

JO - Inorganic Chemistry

T2 - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -

Martens CF, Schenning APHJ, Feiters MC, Berens HW, van der Linden JGM, Admiraal G et al. X-ray structures and redox properties of Copper(II) Bis(pyrazole) complexes. Inorganic Chemistry. 1995 Sep 1;34(19):4735-4744. Available from, DOI: 10.1021/ic00123a005