Novel oxorhenium complexes with 2-(2′-hydoxy-5′-methylphenyl)benzotriazolato ligand. X-ray studies, spectroscopic characterization and DFT calculations

The [ReOCl2(hmpbta)(AsPh3)] · MeCN, [ReOBr2(hmpbta)(AsPh3)] · MeCN, [ReOCl2(hmpbta)(PPh3)] · MeCN, [ReOBr2(hmpbta)(PPh3)] · MeCN, and [ReBr2(hmpbta)(PPh3)] · MeCN complexes have been prepared in the reactions of [ReOX3(EPh3)2] (X = Cl, Br; E = P, As) with 2-(2’-hydoxy-5′-methylphenyl)benzotriazole in molar ratio 1:1. All the compounds were structurally and spectroscopically characterized. The electronic structure of [ReOCl2(hmpbta)(AsPh3)] has been calculated with the density functional theory (DFT) method. The TDDFT/PCM calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase, and the UV–Vis spectrum of [ReOCl2(hmpbta)(AsPh3)] has been discussed on this basis. The paper reports also X-ray structure and DFT calculations for the disubstituted [ReOCl(hmpbta)2] chelate.

Graphical abstractThe [ReOCl2(hmpbta)(AsPh3)]·MeCN, [ReOBr2(hmpbta)(AsPh3)]·MeCN, [ReOCl2(hmpbta)(PPh3)]·MeCN, [ReOBr2(hmpbta)(PPh3)]·MeCN, [ReBr2(hmpbta)(PPh3)]·MeCN complexes have been prepared in the reactions of [ReOX3(EPh3)2] (X=Cl, Br; E=P, As) with 2-(2’-hydoxy-5’-methylphenyl)benzotriazole in molar ratio 1:1. All the compounds were structurally and spectroscopically characterised. The electronic structure of [ReOCl2(hmpbta)(AsPh3)] has been calculated with the density functional theory (DFT) method. The TDDFT/PCM calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase, and the UV-Vis spectrum of [ReOCl2(hmpbta)(AsPh3)] has been discussed on this basis. The paper reports also X-Ray structure and DFT calculations for the disubstituted [ReOCl(hmpbta)2] chelate.Figure optionsDownload full-size imageDownload as PowerPoint slide