Both Mn(CO)5 and Mn2(CO)9 are observed following gas-phase photolysis of Mn2(CO)10. The Mn(CO)5/Mn2(CO)9 ratio can be shifted to favor formation of Mn2(CO)9 by increasing the photolysis energy from 351 to 248 to 193 nm. Mn(CO)5 is formed with significant amounts of internal excitation. Further, as the photolysis energy increases, additional photoproducts are produced which are tentatively assigned as predominantly Mn2(CO)x species (x < 9). IR absorptions of both Mn(CO)5 and Mn2(CO)9 have been recorded and assigned in the range ~2050 to ~ 1750 cm-1. The rate constant for the reaction of two Mn(CO)5 radicals to form Mn2(CO)l0 has been measured and found to be near gas kinetic. The rate constant for the reaction of Mn2(CO)9 with CO to form Mn2(CO)l0 has been determined to be (2.4 ± 0.8) × 106 L mol-1 s-1.
ASJC Scopus subject areas
- Colloid and Surface Chemistry