Rhenium dimers oxidation

Two intermediate oxidation-state rhenium dimers containing the Ref moiety have been structurally characterized with metal-metal separations of... 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Olefin metathesis is the transition-metal-catalyzed inter- or intramolecular exchange of alkylidene units of alkenes. The metathesis of propene is the most simple example in the presence of a suitable catalyst, an equilibrium mixture of ethene, 2-butene, and unreacted propene is obtained (Eq. 1). This example illustrates one of the most important features of olefin metathesis its reversibility. The metathesis of propene was the first technical process exploiting the olefin metathesis reaction. It is known as the Phillips triolefin process and was run from 1966 till 1972 for the production of 2-butene (feedstock propene) and from 1985 for the production of propene (feedstock ethene and 2-butene, which is nowadays obtained by dimerization of ethene). Typical catalysts are oxides of tungsten, molybdenum or rhenium supported on silica or alumina [ 1 ]. 

Rhenium(III) complexes with sulfur dioxide ligands have been obtained by oxidation of dimeric sulfido-bridged complexes either by air or by NO(PFe). The oxidation of the bridging sulfur atoms is facilitated by the high electron density at these ligands. 

For Re2(02CC Hs)4Cl2 the first reduction wave near —0.3 V is quasi-reversible. The product of this one-electron oxidation was not isolated as a solid, but ESR spectra were obtained on frozen dichloromethane solutions at 77°K at both X- and Q-band frequencies. Both naturally occurring rhenium isotopes have a nuclear spin of 5/2 with slightly different nuclear magnetic moments. For dimeric rhenium species there are three distinct isotopic isomers and each generates a unique ESR spectrum as a result of differing hyperfine interactions. The observed ESR spectrum is a superposition of these lines with the intensity... 

A novel oxidative ring-opening dimerization of tetrahydrofuran with acids was catalyzed by Re207 to produce unsymmetrical diesters, as represented by the following example <07JA1246>. This reaction, in which an oxygen atom of the rhenium oxide is transferred to the ester product, is unique to tetrahydrofuran itself. 

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