Non-stoichiometric chloride salts of dioxotetrakis(imidazole)rhenium(V) cations

• Anne-Marie Lebuis

• Jim M.C. Young

• André L. Beauchamp

抄録

Orange [ReO 2 L 4 ]Cl salts were prepared with L = imidazole and 2-methylimidazole. The presence of a strong Re = O stretching band in the infrared spectra near 785 cm −1 is consistent with a trans-dioxo octahedral structure. With 1,2-dimethylimidazole, red-violet solids were obtained, which were studied by X-ray diffraction. Form I (from methanol): cubic, [Formula: see text]a = 25.205 Å, R = 0.032, 986 observed reflections; form II (from ethanol-dichloromethane): cubic, [Formula: see text]a = 25.520 Å, R = 0.056, 766 observed reflections. Both materials are non-stoichiometric, containing trans-[ReO 2 L 4 ] + and protonated trans-[ReO(OH)L 4 ] 2+ in an approximate ratio of 3:1 for 1 and 2:1 for II. In both cases, the unit cell contains 1 "normal" Cl − ion and 2/3 H 2 O per complex. In form I, the additional charge of [ReO(OH)L 4 ] 2+ is balanced by an extra Cl − ion partly occupying the unit cell origin, where it is replaced by disordered methanol the rest of the time. In form II, ReO 4 − and CH 2 Cl 2 play the corresponding roles. In the infrared spectra, besides the characteristic band for the dioxo species, both forms show an extra peak at ~932 cm −1 originating from the protonated species, whereas form II shows an additional band at 907 cm −1 for uncoordinated ReO 4 − . The 1 H and 13 C NMR spectra of both forms in D 2 O are identical to those of the pure [ReO 2 L 4 ] + salt, indicating that the protonated species is strongly acidic.

収録刊行物

• Canadian Journal of Chemistry

  Canadian Journal of Chemistry 71 (12), 2070-2078, 1993-12-01

  Canadian Science Publishing

キーワード

• Organic Chemistry
• General Chemistry
• Catalysis

詳細情報

• CRID: 1362544418397511936
• NII論文ID: 30021731365
• DOI: 10.1139/v93-257
• ISSN: 14803291
• ISSN: 00084042
• Web Site: http://www.nrcresearchpress.com/doi/pdf/10.1139/v93-257
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