130950-24-2Relevant academic research and scientific papers
Photochemical reaction of dinuclear manganese carbonyl compounds with tributyltin hydride and with silanes
Sullivan, Richard J.,Brown, Theodore L.
, p. 9155 - 9161 (1991)
The photochemical reactions of Mn2(CO)8L2 (L = CO, PMe3, P(n-Bu)3, P(i-Pr)3) with HSnBu3 or HSiEt3 in hexane solutions have been studied, using 366- or 313-nm irradiation, and under CO or Ar atmospheres. Under CO, 1.1-3.7 atm, the products of the reaction of Mn2(CO)10 with HSnBu3 are HMn(CO)5 and Bu3SnMn(CO)5. Under Ar or low CO pressures, a third product, assigned as HMn(CO)4(SnBu3)2, is formed at the expense of Bu3SnMn(CO)5. For a given photon flux, the reaction rate is inversely related to [CO]. The behavior of the system is consistent with a reaction pathway that involves oxidative addition of the hydride to the coordinatively unsaturated metal center formed upon CO loss. Analogous results are observed for the phosphine-substituted manganese carbonyl dinners. Reaction with HSiEt3 proceeds much more slowly under equivalent conditions of irradiation. In the reaction with Mn2(CO)5, only HMn(CO)5 is seen as a significant product, with trace amounts of Et3SiMn(CO)5 also observed. These results are also consistent with oxidative addition to the Co-loss product as the only pathway for the photochemical reaction. None of the manganese dimers undergo photochemical reaction with either fluorene or triphenylmethane, in spite of the comparatively low C-H bond energy in each case.
