skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal-quinone complexes

Abstract

Semiquinone and catecholate complexes of vanadium have been studied with tetrachloroquinone and 3,5-di-tert-butylquinone ligands. Crystallographic characterization has been carried out on the sodium salt of V(DBCat)/sub 3//sup -/, obtained as the methanol solvate, Na(V(DBCat)/sub 3/) x 4CH/sub 3/OH. The complex crystallizes in the triclinic space group P1 with Z = 2 in a unit cell of dimensions a = 12.020 (3) A, b = 15.842 (3) A, c = 15.521 (4) A, ..cap alpha.. = 105.04/sup 0/, ..beta.. = 104.94 (2)/sup 0/, ..gamma.. = 110.72 (4)/sup 0/, and V = 2461.7 (8) A/sup 3/. Spectral characterization on Na(V(Cl/sub 4/Cat)/sub 3/) indicates that it has a similar charge distribution. In the solid state, neutral V(Cl/sub 4/SQ)/sub 3/ has the tris semiquinonato)vanadium(III) charge distribution found also with the Cr and Fe analogues. Electrochemical reduction of this complex occurs reversibly in acetonitrile solution, pointing to a change in charge distribution. Under these conditions the form of the complex appears to be V(Cl/sub 4/SQ)(Cl/sub 4/Cat)/sub 2/, containing mixed-charge quinone ligands and related to the solid-state form by transfer of two electrons from the metal to the quinones. Parameters that influence charge distribution in metal-quinone complexes include solvation effects and overall charge of the complexmore » in addition to effects that directly alter d-orbital energy at the metal.« less

Authors:
; ;
Publication Date:
Research Org.:
Univ. of Colorado, Boulder
OSTI Identifier:
7222735
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 25:22
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; PYROCATECHOL; CHARGE DISTRIBUTION; CRYSTAL STRUCTURE; REDUCTION; QUINONES; VANADIUM COMPLEXES; ENERGY LEVELS; EXPERIMENTAL DATA; LIGANDS; SOLVATION; SPACE GROUPS; AROMATICS; CHEMICAL REACTIONS; COMPLEXES; DATA; DEVELOPERS; HYDROXY COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; PHENOLS; POLYPHENOLS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Cass, M E, Gordon, N R, and Pierpont, C G. Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal-quinone complexes. United States: N. p., 1986. Web. doi:10.1021/ic00242a027.
Cass, M E, Gordon, N R, & Pierpont, C G. Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal-quinone complexes. United States. doi:10.1021/ic00242a027.
Cass, M E, Gordon, N R, and Pierpont, C G. Wed . "Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal-quinone complexes". United States. doi:10.1021/ic00242a027.
@article{osti_7222735,
title = {Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal-quinone complexes},
author = {Cass, M E and Gordon, N R and Pierpont, C G},
abstractNote = {Semiquinone and catecholate complexes of vanadium have been studied with tetrachloroquinone and 3,5-di-tert-butylquinone ligands. Crystallographic characterization has been carried out on the sodium salt of V(DBCat)/sub 3//sup -/, obtained as the methanol solvate, Na(V(DBCat)/sub 3/) x 4CH/sub 3/OH. The complex crystallizes in the triclinic space group P1 with Z = 2 in a unit cell of dimensions a = 12.020 (3) A, b = 15.842 (3) A, c = 15.521 (4) A, ..cap alpha.. = 105.04/sup 0/, ..beta.. = 104.94 (2)/sup 0/, ..gamma.. = 110.72 (4)/sup 0/, and V = 2461.7 (8) A/sup 3/. Spectral characterization on Na(V(Cl/sub 4/Cat)/sub 3/) indicates that it has a similar charge distribution. In the solid state, neutral V(Cl/sub 4/SQ)/sub 3/ has the tris semiquinonato)vanadium(III) charge distribution found also with the Cr and Fe analogues. Electrochemical reduction of this complex occurs reversibly in acetonitrile solution, pointing to a change in charge distribution. Under these conditions the form of the complex appears to be V(Cl/sub 4/SQ)(Cl/sub 4/Cat)/sub 2/, containing mixed-charge quinone ligands and related to the solid-state form by transfer of two electrons from the metal to the quinones. Parameters that influence charge distribution in metal-quinone complexes include solvation effects and overall charge of the complex in addition to effects that directly alter d-orbital energy at the metal.},
doi = {10.1021/ic00242a027},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 25:22,
place = {United States},
year = {1986},
month = {10}
}