Reactivity of [ReOX 3(PPh 3) 2] complexes towards pyridazine. X-ray structures of [{ReOCl 2} 2(μ-O)(μ-pyd) 2] · C 6H 6 and [{ReOBr 2} 2(μ-O)(μ-pyd) 2] · CH 3CN, and DFT calculations for [{ReOCl 2} 2(μ-O)(μ-pyd) 2

Abstract

The reactions of the [ReOX 3(PPh 3) 2] (X = Cl, Br) complexes with pyridazine (pyd) have been examined and [{ReOX 2} 2(μ-O)(μ-pyd) 2] dinuclear oxocomplexes with a bent Re 2 O 3 4 + core have been obtained. The X-ray structures of [{ReOCl 2} 2(μ-O)(μ-pyd) 2] · C 6H 6 ( 1 · C 6H 6) and [{ReOBr 2} 2(μ-O)(μ-pyd) 2] · CH 3CN ( 2 · CH 3CN) have been determined. The electronic structure of 1 has been calculated with the density functional theory (DFT) method, and additional information about binding in the Re 2 O 3 4 + unit has been obtained by NBO analysis. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of [{ReOCl 2} 2(μ-O)(μ-pyd) 2] has been discussed on this basis.