Wavelength-, medium-, and temperature-dependent competition between photosubstitution and photofragmentation in Ru/sub 3/(CO)/sub 12/ and Fe/sub 3/(CO)/sub 12/: detection and characterization of coordinatively unsaturated M/sub 3/CO)/sub 11/ complexes

Journal Article · Wed Jul 22 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00249a016· OSTI ID:6084588

Bentsen, J G; Wrighton, M S

This article reports results concerning the photochemical generation of reactive intermediates from visible and near-UV irradiation of M/sub 3/(CO)/sub 12/ (M = Fe, Ru) in low-temperature fluid solutions and in rigid organic solvents. A wavelength, medium, and temperature dependent competition between dissociative loss of CO and fragmentation enables selective photogeneration of coordinatively unsaturated M/sub 3/(CO)/sub 11/ (M = Fe, Ru) fragments with near-UV irradiation of M/sub 3/(CO)/sub 12/ in methylcyclohexane glasses according to eq 1 or, alternatively, reactive dinuclear Ru adducts of ..pi..-acceptor ligands (L = CO and C/sub 2/H/sub 4/) but not PPh/sub 3/ with visible light irradiation of Ru/sub 3/(CO)/sub 12/ in low-temperature alkane solutions according to eq 2. Equation 1 is M/sub 3/(CO)/sub 12/ ..-->../sub M = Fe,Ru//sup hr, 90 K/ M/sub 3/(CO)/sub 11/ + CO and equation 2 is Ru/sub 3/(CO)/sub 12/ ..-->../sub L = CO, C/sub 2/H/sub 4///sup hr, 195 K/ Ru(CO)/sub 4/L + Ru/sub 2/(CO)/sub 8/L.

• Research Organization: Massachusetts Institute of Technology, Cambridge
• OSTI ID: 6084588
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
CARBONYLS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISPERSIONS
EXPERIMENTAL DATA
INFORMATION
IRON COMPLEXES
LOW TEMPERATURE
MIXTURES
NUMERICAL DATA
ORGANIC SOLVENTS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REACTION INTERMEDIATES
RUTHENIUM COMPLEXES
SOLUTIONS
SOLVENTS
TRANSITION ELEMENT COMPLEXES