The photosubstitution reactions of Fe(CO)5 with alcohols and triethylphosphine have been studied
in room temperature solution using femtosecond UV pump IR probe techniques. The dynamics of Fe(CO)5 in
alcohols show that the coordination of the hydroxyl group of the solvent with triplet Fe(CO)4 is generally
much faster than the coordination timescale observed with comparable singlet species. The physical reason
for this is the fact that the metal C−H agostic bond is much weaker for triplets, thus allowing fast rearrangement
to the hydroxyl group of the alcohol. In the case of triethylphosphine photosubstitution, the reaction is divided
into parallel channels which include intersystem crossing and a spin conserving double carbonyl loss. The
intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical
calculations.
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