335000-95-8Relevant articles and documents
Reactions of dithiolate ligands in mononuclear complexes of rhenium(V)
Kanney,Noll,DuBois, M. Rakowski
, p. 9878 - 9886 (2002)
The thermal reactions of the Re(V) dithiolate complex Cp′ReCl2(SCH2CH2S), 1 (where Cp′ = EtMe4C5), and related derivatives have been studied. When 1 is heated in toluene in a sealed evacuated tube at 100°C, a dehydrogenation reaction occurs to form a new rhenium complex with a dithiolene ligand, Cp′ReCl2(SCHCHS), 6, in ca. 40% yield. The structure of 6 has been confirmed by an X-ray diffraction study. Under the thermal conditions studied, 1 also undergoes an olefin extrusion reaction. Free ethene is detected in the NMR spectrum of the products, and insoluble rhenium products are also formed. When 1 is reacted with excess ethene under mild conditions, a new organic product, 1,4-dithiane, is formed. Complex 1 is also found to react with oxidants, such as O2 and S8, under mild conditions to form the dehydrogenation product 6. Kinetic studies of the thermal reaction of 1 and related derivatives have been completed, and possible mechanisms for the thermally induced dehydrogenation reaction are discussed.
