Photolysis of CpMn(CO)3 in neat Et3SiH at ambient temperatures results in the initial generation of CpMn(CO)2 in two spin states, with differing geometries, selectivities, and rates of reaction. While the apparent rate- determining step for the activation of triethylsilane for singlet CpMn(CO)2 and CpRe(CO)2 is the dissociative rearrangement of the ethyl-bound solvate, triplet CpMn(CO)2 interacts only weakly with the solvent C-H bonds, allowing facile reorientation of Et3SiH until the strongly coupling Si-H bond is encountered. The identities of transient species detected by ultrafast infrared spectroscopy were assigned with the aid of ab initio theoretical methods.
|Original language||English (US)|
|Number of pages||8|
|State||Published - May 1 1999|
All Science Journal Classification (ASJC) codes
- Molecular Biology