DFT Investigation of the Mechanism of Phosphine-Thioether Isomerization in the Triosmium Cluster Os-3(CO)(10)(Ph2PCH2CH2SMe): Migratory Preference for the Formation of an Edge-Bridged Thioether versus a Phosphine Moiety
The rearrangement of the phosphine-thioether ligand in 1,2-(P-eq,S-eq)-Os-3(CO)(10)(Ph2PCH2CH2SMe) to 1,1-(P-eq,S-ax)-Os-3(CO)(10)(Ph2PCH2CH2SMe) was investigated by electronic structure calculations. The chelated isomer lies 2.5 kcal/mol lower in energy than its bridged counterpart, and the barrier computed for the mechanism is in agreement with the results from our earlier experimental study. Ph
