Quantitative Photochemistry of (eta(5)-C(5)H(5))Fe(CO)(2)I in Solution: Effective Heterolytic Fe-I Dissociation upon Long-Wavelength Excitation.
The quantitative photochemistry of (eta(5)-C(5)H(5))Fe(CO)(2)I in room-temperature solution involving the heterolytic cleavage of iodide to form (eta(5)-C(5)H(5))Fe(CO)(2)(eta(1)-N-pyrrolyl) has been investigated following irradiation at several wavelengths in the 488-647 nm region. The most effective photoconversions were found to take place with excitation at long wavelengths (580-647 nm) into weak low-lying absorption bands; the absolute quantum efficiency for the photoreaction of (eta(5)-C(5)H(5))Fe(CO)(2)I in room-temperature toluene has been determined to be 0.38 (+/-0.02) upon Kr(+) laser photolysis at 647 nm. The photochemical results are in accordance with recent assignments for the HOMO orbitals in (eta(5)-C(5)H(5))Fe(CO)(2)I and demonstrate that long-wavelength irradiation provides a valuable way of effecting heterolytic Fe-I dissociation, facilitating a synthetic pathway to azaferrocene.
Borja
Charlene E.
CE
Department of Chemistry, State University of New York at Binghamton, Binghamton, New York 13902-6016.
Jakúbek
Vladimír
V
Lees
Alistair J.
AJ