Reactions of phenylbis(2-pyridyl)phosphine with oxorhenium(v) complexes

[ReOCl3(PPh3)2] reacts with phenylbis(2-pyridyl)phosphine (PPhpy2) in boiling THF under the formation of the rhenium(III) compound [ReCl3(PPh3)(OPPhpy2-O,N)]. Reduction of the metal can be avoided by milder reaction conditions, and an asymmetric, oxo-bridged rhenium(V) dimer of the composition (NBu4)[Re2O2Cl5(μ-PPhpy2-P,N,N′)(μ-O)] is obtained from the reaction of PPhpy2 and (NBu4)[ReOCl4] in THF at room temperature. The products have been characterized spectroscopically and by X-ray structure analyses.