Mo(CO)6-Catalyzed Reduction of N,N-Dimethylthioformamide by Silanes, Germanes, and Stannanes (R3EH) To Produce Trimethylamine and Group 14 Thioethers (R3E–S–ER3)

Treatment of N,N-dimethylthioformamide (DMTF) with a variety of silanes, germanes, and stannanes (R3EH; E = Si, Ge, Sn) in the presence of Mo­(CO)6 leads to facile reduction to trimethylamine and the corresponding group 14 thioethers, (R3E)2S. In the reactions we are able to observe the intermediacy of the catalytically active Mo­(CO)5(SCHNMe2) and completely characterize it, including single-crystal X-ray structural analysis. In the case of R3SnH, the reduction occurs without the need for a metal catalyst, presumably via a free radical process.