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

• Published in: Polyhedron Vol. 40; no. 1; pp. 93 - 104
• Main Authors: Machura, B., Wolff, M., Gryca, I., Kruszynski, R.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 19.06.2012
• Subjects: Benzothiazole; DFT calculations; NBO analysis; Oxorhenium(V) complexes; X-ray crystal structures; X-ray crystal structures; Oxorhenium(V) complexes; Benzothiazole; DFT calculations; NBO analysis
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2012.03.035

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. [Display omitted] ► 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. 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.