Structural and DFT/TD-DFT investigation of tris(bidentate) complexes of rhenium(III) synthesized from the cis-[ReO2]+ core and benzenethiol derivatives

The reaction of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) complexes [Re(Hatp)(ibsq)2]·OPPh3, [Re(sbsq)3]·OPPh3 and [Re(obsq)3]·OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate) respectively. These paramagnetic complexes were characterized by single crystal X-ray crystallography, 1H NMR spectrometry, IR and electronic spectroscopy, and cyclic voltammetry. To complement the experimental data, density functional theory (DFT) and time-dependent DFT were successfully used to investigate the structural, molecular, infrared and electronic spectra of these three complexes.

Graphical abstractThe reaction of the rhenium(V) complex cis-[ReO2I(PPh3)2] with 2-aminothiophenol (H2atp), benzene-1,2-dithiol (H2tdt) and 2-hydroxybenzenethiol (H2otp) led to the formation of the rhenium(III) complexes [Re(Hatp)(ibsq)2]·OPPh3, [Re(sbsq)3]·OPPh3 and [Re(obsq)3]·OPPh3 (ibsq = 2-iminothiobenzosemiquinonate, sbsq = 1,2-dithiobenzosemiquinonate, obsq = 2-hydroxothiobenzosemiquinonate), respectively.Figure optionsDownload full-size imageDownload as PowerPoint slide