FT-EPR study of alkyl radicals formed in the photochemical reaction of Re(alkyl)(alpha-diimine) and Ru(alkyl)(alpha-diimine) complexes

A Fourier transform EPR (FT-EPR) study was made of the photochemistry of [R e(R)(CO)(3) (alpha-diimine)] and [Ru(E)(R)(CO)(2)(alpha-diimine)] complexes , where R = alkyl or benzyl, E = I or SnPh3, and a-diimine = 4,4'-dimethyl- 2,2' -bipyridine (DMB) or N,N'-diisopropyl-1,4-diazabutadiene (iPr-DAB). Ph otoexcitation of these complexes leads to homolysis of the metal-alkyl (ben zyl) bonds as evident from the detection of the spectra of the alkyl (benzy l) radicals. FT-EPR spectra display strong spin polarization effects attrib uted to Triplet Mechanism (TM) and Radical Pair Mechanism (RPM) Chemically Induced Dynamic Electron Polarization (CIDEP). CIDEP patterns point to bond dissociation via a triplet state precursor For a number of complexes, spin polarization was found to exhibit unusually large solvent effects, whereas for one complex the CIDEP pattern proved to be sensitive to the wavelength of laser light used to initiate bond dissociation. These effects reflect t he strong dependence of CIDEP on the character of the excited states involv ed in the photochemical reactions and contribute to the understanding of th e reaction mechanism.