Reactions of Organozinc Thiolates with Nitrosonium Ion: C-Nitroso Formation by Possible Transnitrosation

The organometallic complexes [ZnPAThEt] and [ZnPAThMes], where PATh is 2-methyl-1-[methyl-(2-pyridin-2-yl-ethyl)amino]propane-2-thiolate, were prepared and their reactions with NOBF4 investigated. Formation of C-nitrosoethane and C-nitrosomesitylene, respectively, was established, and structural characterization of the latter by X-ray crystallography conclusively proved the dimeric nature of [MesNO](2) in the solid state. A transnitrosation pathway for C-nitroso formation is proposed based on theoretical calculations.