Time resolved studies of bond activation by organometallic complexes

Abstract

In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H){sub 2}L (Cp* = (CH{sub 3}){sub 5}C{sub 5}, L = PPh{sub 3}, Ph = C{sub 6}H{sub 5}) to form Cp*ML(R)(H) or of Cp*Ir(CO){sub 2} to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.