Tungsten complexes, photochemistry

I.r. laser techniques have been used to study [Fe(CO)4] in a nitrogen matrix at 20 K. Surprisingly, the quantum yield for intramolecular isomerization is greato-than the quantum yield for formation of [Fe(CO)4(N2)]. Photolysis of matrix isolated [Mo(CO)s] in the presence of Na at 20 K affords [Mo(CO)5Na)]. Under similar conditions, the analogous chromium and tungsten complexes have been detected by i.r. and Raman techniques. The photochemistry of [O(C0)5] and related species in matrices has been studied via polarized light spectroscopy. A mechanism has been proposed which accounts for almost all the experimental data on matrix-isolated [M(CO)s] (M=Cr, Mo, or W), [M(CO)5(Na)], and [M(CO)4(CS)]. Reactions occur via the following steps ... 

Photochemistry. For photochemical experiments, each MPe complex was dissolved in nitrogen-saturated dichloromethane, which contained 10 M CBr4 as the electron acceptor. The solutions were irradiated with light from a 300 W tungsten-halogen projector lamp and excitation into the... 

The photochemistry of dithiolene complexes of selected second- and third-row transition metal ions have also been investigated. Like the complexes with nickel, dithiolene complexes of palladium, platinum, molybdenum, and tungsten catalyze the formation of hydrogen from water when aqueous solutions of the complexes are irradiated at wavelengths shorter than 290 Tetrahydrofiiran is... 

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