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.