Mechanism of the Photochemical Ligand Substitution Reactions of fac-[Re(bpy)(CO)3(PR3)]+ Complexes and the Properties of Their Triplet Ligand-Field Excited States

• Published in: Journal of the American Chemical Society Vol. 124; no. 38; pp. 11448 - 11455
• Main Authors: KOIKE, Kazuhide, OKOSHI, Nobuaki, HORI, Hisao, TAKEUCHI, Koji, ISHITANI, Osamu, TSUBAKI, Hideaki, CLARK, Ian P., GEORGE, Michael W., JOHNSON, Frank P. A., TURNER, James J.
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 25.09.2002
• Subjects: Chemistry; Exact sciences and technology; General and physical chemistry; Photochemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Cationic complex; Ligand substitution; Tertiary phosphine; Electronically excited state; Organic ligand; Transition metal Carbonyl Complexes; NMR spectrometry; Photochemical reaction; Experimental study; Intramolecular charge transfer; Organic solvent; Near ultraviolet radiation; Rhenium Carbonyl Complexes; Complexes Mixed; Thermodynamic parameter; Reaction mechanism; Photochemical stability; Kinetic parameter; Rate constant; Ultraviolet visible spectrometry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja017032m

We report herein the mechanism of the photochemical ligand substitution reactions of a series of fac-[Re(X(2)bpy)(CO)(3)(PR(3))](+) complexes (1) and the properties of their triplet ligand-field ((3)LF) excited states. The reason for the photostability of the rhenium complexes [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) was also investigated. Irradiation of an acetonitrile solution of 1 selectively gave the biscarbonyl complexes cis,trans-[Re(X(2)bpy)(CO)(2)(PR(3))(CH(3)CN)](+) (2). Isotope experiments clearly showed that the CO ligand trans to the PR(3) ligand was selectively substituted. The photochemical reactions proceeded via a dissociative mechanism from the (3)LF excited state. The thermodynamical data for the (3)LF excited states of complexes 1 and the corrective nonradiative decay rate constants for the triplet metal-to-ligand charge-transfer ((3)MLCT) states were obtained from temperature-dependence data for the emission lifetimes and for the quantum yields of the photochemical reactions and the emission. Comparison of 1 with [Re(X(2)bpy)(CO)(3)(py)](+) (3) and [Re(X(2)bpy)(CO)(3)Cl] (4) indicated that the (3)LF states of some 3- and 4-type complexes are probably accessible from the (3)MLCT state even at ambient temperature, but these complexes were stable to irradiation at 365 nm. The photostability of 3 and 4, in contrast to 1, can be explained by differences in the trans effects of the PR(3), py, and Cl(-) ligands.