86665-07-8Relevant academic research and scientific papers
PHOTOCHEMISTRY OF TRICARBONYL(α-DI-IMINE)IRON COMPLEXES. NEW MECHANISTIC ASPECTS FOR CO PHOTOSUBSTITUTION IN SOLUTION AND EVIDENCE FOR ?,?-CO -ORDINATION OF 1,4-DIAZA-1,3-BUTADIENE LIGANDS IN MATRICES AT 10 K
Kookkes, Maarten W.,Stufkens, Derk J.,Oskam, Ad
, p. 1005 - 1018 (2007/10/02)
The metal-to-ligand charge-transfer photochemistry of (Fe(CO)3(α-di-imine)) has been studied in detail.For (Fe(CO)3L) (L=1,4-diaza-1,3-butadiene, RN=CH-CH=NR) CO photosubstitution takes place with high quantum yield (Φ=0.2) in solution via a partial dissociation of L.In matrices at 10 K, a changeover from ?,?-N,N'-to ?,?-co-ordination is found as primary step in the photolysis of (Fe(CO)3L) complexes.The resulting (Fe(CO)3(?,?-L)) decomposes thermally to a (Fe(CO)2(?,?-N,N'-L)) fragment with simultaneous release of CO.For (Fe(CO)3(dpipy)) (dpipy=2-(2',6'-di-isopropylphenylimino)pyridine) no ?,?-co-ordination is observed.A 13CO-labelling force field calculation has been performed for a (Fe(CO)3L) complex and its photolysis product (Fe(CO)2(?,?,-N,N'-L)), showing two structurally different conformers of the latter product.The different photochemical behaviour in solution and in a matrix is discussed and a mechanism is proposed for the photosubstitutional reactions in solution.
