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

Journal Article · Wed Oct 22 04:00:00 EDT 1986 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00242a027· OSTI ID:7222735

Cass, M E; Gordon, N R; Pierpont, C G

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.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 7222735
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:22; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AROMATICS
CHARGE DISTRIBUTION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DEVELOPERS
ENERGY LEVELS
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHENOLS
POLYPHENOLS
PYROCATECHOL
QUINONES
REDUCTION
SOLVATION
SPACE GROUPS
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES