Reporting a Unique Example of Electronic Bistability Observed in the Form of Valence Tautomerism with a Copper(II) Helicate of a Redox-Active Nitrogenous Heterocyclic Ligand

Valence tautomeric compounds involving nondixolene-type ligands are rare. The triple-helicate copper(II) complex [CuII 2(L)3](ClO4)4·3CH3CN (1) containing a redox-active N-heterocyclic ligand (L) has been prepared and displays VT equilibrium in solution, as established by electronic spectroscopy, el...

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 133; no. 50; pp. 20104 - 20107
Main Authors Kundu, Nabanita, Maity, Manoranjan, Chatterjee, Pabitra Baran, Teat, Simon J, Endo, Akira, Chaudhury, Muktimoy
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 21.12.2011
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
CATECHOLATE
OXIDATION
TRANSITION-METAL-COMPLEXES
TEMPERATURE
SEMIQUINONE
QUINONE COMPLEXES
CHARGE-DISTRIBUTION
X-RAY-ABSORPTION
INTERCONVERSION
THERMAL HYSTERESIS
Online AccessGet full text

Cover

More Information
Summary:Valence tautomeric compounds involving nondixolene-type ligands are rare. The triple-helicate copper(II) complex [CuII 2(L)3](ClO4)4·3CH3CN (1) containing a redox-active N-heterocyclic ligand (L) has been prepared and displays VT equilibrium in solution, as established by electronic spectroscopy, electron paramagnetic resonance spectroscopy, and cyclic and differential pulse voltammetry carried out at variable temperatures. The process involves intramolecular transfer of an electron from one of the L ligands to a copper(II) center, leading to the oxidation of L to an L•+ radical with concomitant reduction of the CuII center to CuI, as shown by the equilibrium [CuIICuIL•+L2]4+ ⇄ [CuII 2L3]4+.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/ja2088986