Rhenium carbonyl semiquinone complexes. Photochemical addition of 9,10-phenanthrenequinone to Re/sub 2/(CO)/sub 10/

Journal Article · Wed Nov 11 04:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00257a021· OSTI ID:7075932

DeLearie, L A; Pierpont, C G

The photochemical reaction between Re/sub 2/(CO)/sub 10/ and 9,10-phenanthrenequinone has been investigated. In contrast with related reactions carried out with other quinones which gave tris(catecholate)rhenium(VI) products, the product obtained in this case is a binuclear rhenium(I) semiquinone carbonyl complex, Re/sub 2/(CO)/sub 7/(PhenSQ)/sub 2/. The complex crystallizes in the triclinic space group P anti 1 in a unit cell with dimensions a = 9.509 (2) A, b = 11.955 (2) A, c = 15.131 (4) A, ..cap alpha.. = 74.36 (2)/sup 0/, ..beta.. = 87.20 (2)/sup 0/, ..gamma.. = 67.00 (2)/sup 0/, and Z = 2. The binuclear complex consists of Re(CO)/sub 4/(PhenSQ) and Re(CO)/sub 3/(PhenSQ) units linked by a bridge formed by one semiquinone oxygen of the chelated ligand of the Re(CO)/sub 4/(PhenSQ) unit. This oxygen bridges to the vacant coordination site of the Re(CO)/sub 3/(PhenSQ) unit. Strong intramolecular interactions between semiquinone ligands further stabilize the dimeric structure in the solid state. This compound is paramagnetic in solution by diamagnetic in the solid state due to magnetic coupling between semiquinone ligands. Electrochemistry shows both chemically reversible two-electron reduction and oxidation couples. Mechanistic implications for the formation of this dimer and the previously characterized tris-chelated rhenium(VI)-catecholate complexes, Re/sup VI/(3,5-DBCat)/sub 3/ and Re/sup VI/(Cl/sub 4/Cat)/sub 3/, are discussed.

• Research Organization: Univ. of Colorado, Boulder (USA)
• OSTI ID: 7075932
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:23; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400 -- Electrochemistry
400500* -- Photochemistry
AROMATICS
CARBONYLS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELECTROCHEMISTRY
EXPERIMENTAL DATA
INFORMATION
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
QUINONES
RHENIUM COMPLEXES
SPACE GROUPS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES