Syntheses, structures, spectroscopic properties and DFT calculations of Re(V)-benzothiazole and 2-(2-aminophenyl)benzothiazole complexes

The paper presents a combined experimental and computational study of novel oxorhenium(V) complexes of benzothiazole (bt) and 2-(2-aminophenyl)benzothiazole (apbt). The complexes [Re2O3Cl4(bt)4]·H2O (1·H2O), [ReO(OEt)Cl2(bt)(PPh3)]·Me2CO (2·Me2CO), [ReO(OPri)Cl2(bt)(PPh3)] (3), [ReOCl2(apbt)(OPPh3)] (4) and [ReOCl2(apbt)(OAsPh3)]·0.5CHCl3 (5·0.5CHCl3) have been characterized structurally (by single-crystal X-ray diffraction) and spectroscopically (by IR, NMR, UV–Vis). For compounds 1, 2 and 4, DFT and TD-DFT calculations have been performed to obtain their IR and UV–Vis absorption spectra, and satisfactory theoretical–experimental agreement was achieved. Additional information about binding between the rhenium atom and oxo ligand in the complexes 1, 2 and 4 has been obtained by NBO analysis.

Novel oxorhenium(V) complexes of benzothiazole (bt) and 2-(2-aminophenyl)benzothiazole (apbt) – [Re2O3Cl4(bt)4]·H2O (1·H2O), [ReO(OEt)Cl2(bt)(PPh3)]·Me2O (2·Me2O), [ReO(OPri)Cl2(bt)(PPh3)] (3), [ReOCl2(apbt)(OPPh3)] (4) and [ReOCl2(apbt)(OAsPh3)] (5·CHCl3) – have been synthesized and characterized structurally (by single-crystal X-ray diffraction) and spectroscopically (by IR, NMR, UV–Vis). For compounds 1, 2 and 4, DFT and TD-DFT calculations have been performed to obtain their IR and UV–Vis absorption spectra, and satisfactory theoretical–experimental agreement was achieved. Additional information about binding between the rhenium atom and oxo ligand in the complexes 1, 2 and 4 has been obtained by NBO analysis.Figure optionsDownload as PowerPoint slideHighlights
► Novel Re(V)-benzothiazole and 2-(2-aminophenyl)benzothiazole complexes were obtained.
► The Re(V) compounds were characterized spectroscopically and structurally.
► The spectroscopic features of the Re(V) complexes were investigated by DFT method.
► The nature of the Re–Ot interaction were studied by NBO analysis.