| Abstract
| - 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 evacuatedtube 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 diffractionstudy. Under the thermal conditions studied, 1 also undergoes an olefin extrusion reaction. Free ethene isdetected in the NMR spectrum of the products, and insoluble rhenium products are also formed. When 1is reacted with excess ethene under mild conditions, a new organic product, 1,4-dithiane, is formed. Complex1 is also found to react with oxidants, such as O2 and S8, under mild conditions to form the dehydrogenationproduct 6. Kinetic studies of the thermal reaction of 1 and related derivatives have been completed, andpossible mechanisms for the thermally induced dehydrogenation reaction are discussed.
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