Solvothermal Approach to the Synthesis of Triangular Re(III) Iodide and Bromide Cluster Complexes

• Published in: Russian journal of inorganic chemistry 2021-07, Vol.66 (7), p.969-974
• Main Authors: Mikhailov, M. A., Sukhikh, T. S., Sokolov, M. N.
• Format: Article
• Language: English
• Subjects: Chemical analysis; Chemistry; Chemistry and Materials Science; Clusters; Crystal structure; Crystallization; Hydrothermal reactions; Inert atmospheres; Inorganic Chemistry; Ligands; NMR spectroscopy; Phosphoric acid; Single crystals; Spectrum analysis; Synthesis and Properties of Inorganic Compounds; Thermal stability; Vibrational spectra; X ray powder diffraction; X-ray diffraction
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023621070081

Crystalline Re 3 I 9 ( 1 ) is formed in a quantitative yield upon the hydrothermal reaction of NaReO 4 with concentrated HI at 200°C. The reaction of Re 3 I 9 with HBr at 200°C results in complete replacement of iodide ligands with bromide ligands with retention of the cluster core. The addition of pyridine to the reaction mixture leads to crystallization of the pyridinium salt (PyH) 2 [Re 3 Br 11 (H 2 O)] · 4H 2 O ( 2 ). In the presence of phosphoric acid, (PyH) 2 [Re 3 Br 9 (PO 4 H)]·H 2 O ( 3 ) and (Et 4 N) 2 [Re 3 Br 9 (PO 4 H)]·2H 2 O ( 4 ) were isolated. The crystal structures of the compounds 2 – 4 were determined by single crystal X-ray diffraction. Complexes 1 and 4 were characterized by powder X-ray diffraction. The Re/halogen ratio for compounds 1 – 4 was determined by energy dispersive spectroscopy. Elemental analysis and 31 P NMR spectroscopy data were obtained for compound 4 , and vibrational spectra were measured for 1 (far-IR range) and 4 (near-IR range). The data for thermal stability in inert atmosphere were obtained for 1 .