Carbonyl rhenium radicals

Without addition of spin traps, the photochemically generated Re(CO) radicals dimerize quickly. More persistent rhenium(0) radicals have been prepared by replacement of two carbonyl groups by bulky phosphines to give the species [Re(CO)3(PR3)2]. The restrictions due to the photochemical route, however, prevents isolation of the products in the solid state. This can be... 

Vanhoye and coworkers [402] synthesized aldehydes by using the electrogenerated radical anion of iron pentacarbonyl to reduce iodoethane and benzyl bromide in the presence of carbon monoxide. Esters can be prepared catalytically from alkyl halides and alcohols in the presence of iron pentacarbonyl [403]. Yoshida and coworkers reduced mixtures of organic halides and iron pentacarbonyl and then introduced an electrophile to obtain carbonyl compounds [404] and converted alkyl halides into aldehydes by using iron pentacarbonyl as a catalyst [405,406]. Finally, a review by Torii [407] provides references to additional papers that deal with catalytic processes involving complexes of nickel, cobalt, iron, palladium, rhodium, platinum, chromium, molybdenum, tungsten, manganese, rhenium, tin, lead, zinc, mercury, and titanium. 

U.v. irradiation of manganese or rhenium carbonyl in tetrafluoroethylene at — 93 °C results in rapid polymer formation, and the presence of tetrafluoroethylene in other vinyl monomers also allows initiation of polymerization by these carbonyls. Addition of photochemically generated Mn(CO)4 to CaF4 to give the o-bonded radical species (OC)4Mn CF2 CF2 is suggested. 

---