A MECHANISTIC STUDY OF THE PHOTOCHEMISTRY OF TRICARBONYL(1-AZA-1,3-BUTADIENE)IRON COMPLEXES IN CH4 MATRICES AT 10 K AND IN SOLUTION AT 293 K

Article abstract of DOI:10.1016/S0022-328X(00)98935-6

The photochemistry has been studied of the complexes 1,Ph-ABD)> (R¹,Ph-ABD represents R¹N=CHCH=CHPh; 1R¹,4Ph-1-aza-1,3-butadiene) both in a CH4 matrix at 10 K and in solution at 293 K.Matrix photolysis of causes breaking of the iron-olefin bond with formation of the 16-electron species .In solution the R¹,Ph-ABD ligand is replaced photochemically by other R¹,Ph-ABD molecules and by R-DAB (R-DAB = 1,4-diaza-1,3-butadiene; RN=CHCH=NR).Photolysis in the presence of PR3 results in the formation of 1,Ph-ABD)(PR3)>, and .The relative amounts of these photoproducts depend on the PR3 concentration, on the R¹,Ph-ABD ligand used, and on the polarity of the solvent.A mechanism is proposed in which the product of the matrix photolysis is assumed to be the primary photoproduct of the photosubstitution reactions.