EurekaMag.com logo
+ Site Statistics
References:
53,869,633
Abstracts:
29,686,251
+ Search Articles
+ Subscribe to Site Feeds
EurekaMag Most Shared ContentMost Shared
EurekaMag PDF Full Text ContentPDF Full Text
+ PDF Full Text
Request PDF Full TextRequest PDF Full Text
+ Follow Us
Follow on FacebookFollow on Facebook
Follow on TwitterFollow on Twitter
Follow on LinkedInFollow on LinkedIn

+ Translate

Trigonal planar copper(I) complex: synthesis, structure, and spectra of a redox pair of novel copper(II/I) complexes of tridentate bis(benzimidazol-2'-yl) ligand framework as models for electron-transfer copper proteins



Trigonal planar copper(I) complex: synthesis, structure, and spectra of a redox pair of novel copper(II/I) complexes of tridentate bis(benzimidazol-2'-yl) ligand framework as models for electron-transfer copper proteins



Inorganic Chemistry 40(10): 2246-2255



The copper(II) and copper(I) complexes of the chelating ligands 2,6-bis(benzimidazol-2'-ylthiomethyl)pyridine (bbtmp) and N,N-bis(benzimidazol-2'-ylthioethyl)methylamine (bbtma) have been isolated and characterized by electronic and EPR spectra. The molecular structures of a redox pair of Cu(II/I) complexes, viz., [Cu(bbtmp)(NO(3))]NO(3), 1, and [Cu(bbtmp)]NO(3), 2, and of [Cu(bbtmp)Cl], 3, have been determined by single-crystal X-ray crystallography. The cation of the green complex [Cu(bbtmp)(NO(3))]NO(3) possesses an almost perfectly square planar coordination geometry in which the corners are occupied by the pyridine and two benzimidazole nitrogen atoms of the bbtmp ligand and an oxygen atom of the nitrate ion. The light-yellow complex [Cu(bbtmp)]NO(3) contains copper(I) with trigonal planar coordination geometry constituted by the pyridine and two benzimidazole nitrogen atoms of the bbtmp ligand. In the yellow chloride complex [Cu(bbtmp)Cl] the asymmetric unit consists of two complex molecules that are crystallographically independent. The coordination geometry of copper(I) in these molecules, in contrast to the nitrate, is tetrahedral, with pyridine and two benzimidazole nitrogen atoms of bbtmp ligand and the chloride ion occupying the apexes. The above coordination structures are unusual in that the thioether sulfurs are not engaged in coordination and the presence of two seven-membered chelate rings facilitates strong coordination of the benzimidazole nitrogens and discourage any distortion in Cu(II) coordination geometry. The solid-state coordination geometries are retained even in solution, as revealed by electronic, EPR, and (1)H NMR spectra. The electrochemical behavior of the present and other similar CuN(3) complexes has been examined, and the thermodynamic aspects of the electrode process are correlated to the stereochemical reorganizations accompanying the redox changes. The influence of coordinated pyridine and amine nitrogen atoms on the spectral and electrochemical properties has been discussed.

(PDF emailed within 0-6 h: $19.90)

Accession: 047843422

Download citation: RISBibTeXText

PMID: 11327898

DOI: 10.1021/ic0003372



Related references

Preparation structure and properties of pseudotetrahedral d 2 d complexes of copper ii nickel ii cobalt ii copper i and zinc ii with geometrically constraining bidentate ligand 2 2' bis 2 imidazolylbiphenyl examination of electron self exchange for the copper i copper ii pair. Journal of the American Chemical Society 112(9): 3452-3464, 1990

Copper i and copper ii complexes of a new tetra dentate chelating ligand containing imidazole and thio ether groups the x ray structure of trigonal bi pyramidal 1 6 bis n benzylimidazol 2 yl 2 5 dithia hexane n n s s bromo copper ii bromide. Journal of the American Chemical Society 104(26): 7556-7560, 1982

Models for copper dioxygen complexes the chemistry of copper ii with some planar tridentate nitrogen ligands. Helvetica Chimica Acta 72(2): 323-337, 1989

Models for Copper-Dioxygen Complexes: The chemistry of copper(II) with some planar tridentate nitrogen ligands. Helvetica Chimica Acta 72(2): 323-337, 1989

Effect of a tridentate ligand on the structure, electronic structure, and reactivity of the copper(I) nitrite complex: role of the conserved three-histidine ligand environment of the type-2 copper site in copper-containing nitrite reductases. Journal of the American Chemical Society 130(19): 6088-6098, 2008

A new copper(II) chelate complex with tridentate ligand: Synthesis, crystal and molecular electronic structure of aqua-(diethylenetriamine-N, N, N)-copper(II) sulfate monohydrate and its fire retardant properties. Journal of Molecular Structure 1095: 34-41, 2015

Synthesis, Characterization, and Single-Crystal EPR Studies of Three Dinuclear Copper(II) Complexes and One Mixed-Valence Tetranuclear Copper(I)-Copper(II) Cluster with an Asymmetric Imidazole-Containing Tripodal Ligand with Copper(II)-Copper(II) Distances between 3.35 and 3.63 Å. Inorganic Chemistry 35(6): 1509-1517, 1996

Models for copper-proteins Structure and properties of dimeric copper and complexes of a tetraamino-tetrathioether ligand. Journal of Inorganic Biochemistry 66(1): 57-61, 1997

Models for copper-proteins: Structure and properties of dimeric copper (I) and (II) complexes of a tetraamino-tetrathioether ligand. Journal of Inorganic Biochemistry 66(1): 57-61, 1997

Models for copper-proteins: Structure and properties of dimeric copper(I) and (II) complexes of a tetraamino-tetrathioether ligand. Journal of Inorganic Biochemistry 66(1): 57-61, 1997

Synthesis, structure, magnetism, and spectroscopic properties of heterobinuclear copper(II)-zinc(II) complexes and their copper(II)-copper(II) analogues in asymmetric ligand environments. Inorganic Chemistry 43(19): 6015-6023, 2004

Model structures for a copper i copper ii redox couple in copper proteins x ray powder structure of bis imidazole copper i per chlorate and crystal structure of bis imidazole copper ii di acetate. Journal of the Chemical Society Chemical Communications (4): 130-131, 1976

Blue copper proteins synthesis spectra and structures of copper i and copper ii hydro tris 3 5 di methyl 1 pyrazolyl borate mercaptide complex active site analogs. Proceedings of the National Academy of Sciences of the United States of America 74(8): 3114-3118, 1977

Synthesis and properties of a tetraaza macrocyclic ligand containing 2-pyridylmethyl pendant arms and its copper(II) and nickel(II) complexes: crystal structure of the copper(II) complex. Polyhedron 17(18): 3227-3234, 1998

Synthesis and structural and spectroscopic characterization of mononuclear copper nitrosyl complexes Models for nitric oxide adducts of copper proteins and copper-exchanged zeolites. Journal of the American Chemical Society 115(24): 11285-11298, 1993