LAUSR

Herein, we exemplify that time-resolved multiple-probe spectroscopy (TRMPS) with infrared detection can be used to observe and quantify the dynamic processes occurring during the solvation of a catalytically competent manganese(I) carbonyl compound. TRMPS has been used to demonstrate that a manganese(I) 2-phenylpyridyl (ppy) complex, [Mn(ppy)(CO)4], undergoes photochemically induced loss of a carbonyl ligand on a sub-picosecond time scale to give solvent (S) complexes of the type, fac-[Mn(ppy)(S)(CO)3] (S = n-C7H16, CH2Cl2, NCMe, C6H5CH3, THF, 1,4-dioxane, n-Bu2O, and DMSO). An excited state, assigned as 3[Mn(ppy)(CO)4], with a lifetime, τ, of ca. 5 ps is also formed as a minor photoproduct. The vibrational modes of the carbonyl ligands in fac-[Mn(ppy)(S)(CO)3] are diagnostic of the nature of the coordinated solvent and allow for the dynamics of solvation within the coordination of the metal to be observed. For example, in the case of THF, initial interactions with the metal occur through a C–H σ-interact...