322640-91-5Relevant academic research and scientific papers
Ruthenium-assisted insertion of isothiocyanates into the silicon-sulfur bond: A comparative study on the reactivity of the S-Si and S-H bonds in CpRu(PPh3)2SX (X = H, SiiPr3) complexes
Kovács, István,Lebuis, Anne-Marie,Shaver, Alan
, p. 35 - 41 (2008/10/08)
CpRu(PPh3)2SSiiPr3 (1) and CpRu(PPh3)2SH (2) reacted with phenyl, p-tolyl, and 1-naphthyl isothiocyanates, as well as with 1,4-phenylene diisothiocyanate, to give the corresponding k2S,S-dithiocarbamato complexes, CpRu(PPh3)S2CNR1R2 (R1 = SiiPr3, R2 = Ph (3a), p-Tol (3b), 1-Naphth (3c); R1 = H, R2 = Ph (3d), 1-Naphth (3e)) and 1,4-[CpRu(PPh3)S2CNR]2C6H 4 (R = SiiPr3 (4a), H (4b)), the result of insertion of the isothiocyanates into the S-Si and S-H bonds, respectively. The reactions of 1 proceed via precoordination of the isothiocyanates to the ruthenium atom, followed by the formation of N-silyl k2S,S-dithiocarbamates. The reactions of 2, at least in part, involve direct nucleophilic addition of the S-H bond to the isothiocyanates via k1S-dithiocarbamato intermediates. Accordingly, CpRu(dppe)SSiiPr3, where ligand exchange does not occur, did not react, but CpRu(dppe)SH reacted with phenyl and 1-naphthyl isothiocyanate to give the corresponding k1S-dithiocarbamato complexes, CpRu(dppe)SC(S)NHR (R = Ph (9a), 1-Naphth (9b)), the reaction with 1-naphthyl isothiocyanate being reversible. The crystal structures of 3c and 4a have been determined by X-ray diffraction.
