title: Efficient Photodissociation of Anions from Benzoyl-Functionalized Ferrocene Complexes.
abstract: Spectroscopic and photochemical studies of several benzoyl-functionalized ferrocene complexes in nonaqueous solvents are reported. Bands observed above 300 nm in the electronic absorption spectrum of the unsubstituted complex, Fe(eta(5)-C(5)H(5))(2), and assigned to ligand field transitions shift to longer wavelengths and intensify upon introduction of a benzoyl group into one or both cyclopentadienide rings. Such behavior suggests that these transitions have acquired some charge-transfer character. Visible-light (546 nm) irradiation of 1,1'-dibenzoylferrocene, III, dissolved in CH(3)CN, CH(3)OH, or ethyl alpha-cyanopropionate causes ring-metal cleavage to produce the benzoylcyclopentadienide ion, C(6)H(5)C(O)C(5)H(4)(-), and the corresponding half-sandwich cationic complex, Fe[(eta(5)-C(5)H(4))C(O)C(6)H(5)](S)(3)(+) (S is solvent). The disappearance quantum yield, phi(dis), for III is 0.45 in CH(3)OH and 0.28 in ethyl alpha-cyanopropionate and is unaffected by the presence of dissolved O(2), added H(2)O (10 000 ppm), or added methanesulfonic acid (30 ppm). 1,1'-Dibenzoylferrocenes containing substitutents on both phenyl rings undergo photoinduced ring-metal cleavage in CH(3)OH with phi(dis) values very similar to that of III, while monobenzoylferrocenes are appreciably less photoreactive. A mechanism that accommodates the photochemical behavior of benzoyl-functionalized ferrocene complexes is discussed. In addition, a previous suggestion concerning the role of III in the photoinitiated anionic polymerization of an alpha-cyanoacrylate monomer is reconsidered in light of the present study.
authors.affiliation: Department of Chemistry, University of Georgia, Athens, Georgia 30602.
authors.forename: Yoshikazu
authors.initials: Y
authors.lastname: Yamaguchi
authors.forename: Charles
authors.initials: C
authors.lastname: Kutal