Dinuclear copper(II) complexes incorporating a novel pyrazolo-based ligand with S- and N-rich coordination spheres

Jeh Li Chou, Jong Pyng Chyn, F. L. Urbach, Dominic F Gervasio

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The new binucleating ligand 3,5-bis(1′-(4′-(2″-pyridyl)-2′-thiabutyl))pyrazole (BLEPH) forms dinuclear Cu11 complexes which are able to bind one additional exogenous bridging molecule such as N3-, C1-, Br- and OH-. Three of these complexes [Cu2(BLEP)(μ-N3)(N3)2] (1); [Cu2(BLEP)(μ-C1)(C1)(H2O)]C1 (2); and [Cu2(BLEP)(μ-Br)(Br)(H2O)]Br (3) were characterized by X-ray single crystal structure analysis. The two copper centers are bridged by the central pyrazolyl group of the BLEP and one azide (in 1), one chloro (in 2) or bromo (in 3) and the side arm of BLEP coordinates to each of the coppers with one pyridyl N and one thia S. Electrochemical studies of these complexes reveal that the redox waves are -247 and 15 mV for 2; -215 and 37 mV for 3 corresponding to the Cu11Cu11/Cu1Cu11 and Cu1Cu11/Cu1Cu1 couples, and -291 mV for 1 corresponding to the Cu11Cu11/Cu1Cu1 process, respectively. The intramolecular magnetic exchange coupling (J = -46.6 cm-1) in the bromo-bridged complex shows weaker antiferromagnetic interaction than the N3-bridged complex. The exchange coupling process through μ2-N3 ligand enhances the net antiferromagnetic interaction. Electronic spectra covering the 12 500-50 000 cm-1 region are also reported for these complexes.

Original languageEnglish (US)
Pages (from-to)2215-2223
Number of pages9
JournalPolyhedron
Volume19
Issue number20-21
DOIs
StatePublished - 2000
Externally publishedYes

Fingerprint

Exchange coupling
Copper
Ligands
copper
ligands
Azides
electronic spectra
Oxidation-Reduction
coverings
Crystal structure
X-Rays
Single crystals
X rays
crystal structure
Molecules
single crystals
molecules
x rays
interactions
hydroxide ion

Keywords

  • Antiferromagnetic interactions
  • Dinuclear
  • Pryrazolyl groups

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Dinuclear copper(II) complexes incorporating a novel pyrazolo-based ligand with S- and N-rich coordination spheres. / Chou, Jeh Li; Chyn, Jong Pyng; Urbach, F. L.; Gervasio, Dominic F.

In: Polyhedron, Vol. 19, No. 20-21, 2000, p. 2215-2223.

Research output: Contribution to journalArticle

Chou, Jeh Li ; Chyn, Jong Pyng ; Urbach, F. L. ; Gervasio, Dominic F. / Dinuclear copper(II) complexes incorporating a novel pyrazolo-based ligand with S- and N-rich coordination spheres. In: Polyhedron. 2000 ; Vol. 19, No. 20-21. pp. 2215-2223.
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abstract = "The new binucleating ligand 3,5-bis(1′-(4′-(2″-pyridyl)-2′-thiabutyl))pyrazole (BLEPH) forms dinuclear Cu11 complexes which are able to bind one additional exogenous bridging molecule such as N3-, C1-, Br- and OH-. Three of these complexes [Cu2(BLEP)(μ-N3)(N3)2] (1); [Cu2(BLEP)(μ-C1)(C1)(H2O)]C1 (2); and [Cu2(BLEP)(μ-Br)(Br)(H2O)]Br (3) were characterized by X-ray single crystal structure analysis. The two copper centers are bridged by the central pyrazolyl group of the BLEP and one azide (in 1), one chloro (in 2) or bromo (in 3) and the side arm of BLEP coordinates to each of the coppers with one pyridyl N and one thia S. Electrochemical studies of these complexes reveal that the redox waves are -247 and 15 mV for 2; -215 and 37 mV for 3 corresponding to the Cu11Cu11/Cu1Cu11 and Cu1Cu11/Cu1Cu1 couples, and -291 mV for 1 corresponding to the Cu11Cu11/Cu1Cu1 process, respectively. The intramolecular magnetic exchange coupling (J = -46.6 cm-1) in the bromo-bridged complex shows weaker antiferromagnetic interaction than the N3-bridged complex. The exchange coupling process through μ2-N3 ligand enhances the net antiferromagnetic interaction. Electronic spectra covering the 12 500-50 000 cm-1 region are also reported for these complexes.",
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T1 - Dinuclear copper(II) complexes incorporating a novel pyrazolo-based ligand with S- and N-rich coordination spheres

AU - Chou, Jeh Li

AU - Chyn, Jong Pyng

AU - Urbach, F. L.

AU - Gervasio, Dominic F

PY - 2000

Y1 - 2000

N2 - The new binucleating ligand 3,5-bis(1′-(4′-(2″-pyridyl)-2′-thiabutyl))pyrazole (BLEPH) forms dinuclear Cu11 complexes which are able to bind one additional exogenous bridging molecule such as N3-, C1-, Br- and OH-. Three of these complexes [Cu2(BLEP)(μ-N3)(N3)2] (1); [Cu2(BLEP)(μ-C1)(C1)(H2O)]C1 (2); and [Cu2(BLEP)(μ-Br)(Br)(H2O)]Br (3) were characterized by X-ray single crystal structure analysis. The two copper centers are bridged by the central pyrazolyl group of the BLEP and one azide (in 1), one chloro (in 2) or bromo (in 3) and the side arm of BLEP coordinates to each of the coppers with one pyridyl N and one thia S. Electrochemical studies of these complexes reveal that the redox waves are -247 and 15 mV for 2; -215 and 37 mV for 3 corresponding to the Cu11Cu11/Cu1Cu11 and Cu1Cu11/Cu1Cu1 couples, and -291 mV for 1 corresponding to the Cu11Cu11/Cu1Cu1 process, respectively. The intramolecular magnetic exchange coupling (J = -46.6 cm-1) in the bromo-bridged complex shows weaker antiferromagnetic interaction than the N3-bridged complex. The exchange coupling process through μ2-N3 ligand enhances the net antiferromagnetic interaction. Electronic spectra covering the 12 500-50 000 cm-1 region are also reported for these complexes.

AB - The new binucleating ligand 3,5-bis(1′-(4′-(2″-pyridyl)-2′-thiabutyl))pyrazole (BLEPH) forms dinuclear Cu11 complexes which are able to bind one additional exogenous bridging molecule such as N3-, C1-, Br- and OH-. Three of these complexes [Cu2(BLEP)(μ-N3)(N3)2] (1); [Cu2(BLEP)(μ-C1)(C1)(H2O)]C1 (2); and [Cu2(BLEP)(μ-Br)(Br)(H2O)]Br (3) were characterized by X-ray single crystal structure analysis. The two copper centers are bridged by the central pyrazolyl group of the BLEP and one azide (in 1), one chloro (in 2) or bromo (in 3) and the side arm of BLEP coordinates to each of the coppers with one pyridyl N and one thia S. Electrochemical studies of these complexes reveal that the redox waves are -247 and 15 mV for 2; -215 and 37 mV for 3 corresponding to the Cu11Cu11/Cu1Cu11 and Cu1Cu11/Cu1Cu1 couples, and -291 mV for 1 corresponding to the Cu11Cu11/Cu1Cu1 process, respectively. The intramolecular magnetic exchange coupling (J = -46.6 cm-1) in the bromo-bridged complex shows weaker antiferromagnetic interaction than the N3-bridged complex. The exchange coupling process through μ2-N3 ligand enhances the net antiferromagnetic interaction. Electronic spectra covering the 12 500-50 000 cm-1 region are also reported for these complexes.

KW - Antiferromagnetic interactions

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KW - Pryrazolyl groups

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