Structural characterization of zirconium isopropoxide precursors modified by di- and trichloroacetic acids

• Published in: Inorganica Chimica Acta 2006-11, Vol.359 (14), p.4511-4518
• Main Authors: Pandey, Ashutosh, Pandey, Anjana, Parak, W.J., Mayer, Peter
• Format: Article
• Language: English
• Subjects: Chloroacetic acid; Isopropoxide; Oxo; Zirconium compounds
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2006.07.005

Di- and Tri- nuclear zirconium isopropoxy chloroacetates have been prepared. Their synthesis, spectral characterization and single crystal X-ray crystallographic structures are reported here. Reactions of Zr(O i Pr) 4(Pr i OH) with di- and trichloroacetic acid in 1:1 molar ratio in toluene gave the products Zr 2(μ-O i Pr) 2(μ-OOCCHCl 2)(O i Pr) 4(OOCCHCl 2)(HO i Pr) ( 1) and Zr 2(μ-O i Pr) 2(μOOCCCl 3)(O i Pr) 4(OOCCCl 3)(HO i Pr) ( 2), respectively, in quantitative yields. The molecular geometry of both ( 1) and ( 2) is constituted by a slightly distorted edge-shared bioctahedron and both have almost similar bond dimensions. Addition of dichloroacetic acid in 1:2 molar ratio to Zr(O i Pr) 4(HO i Pr) in toluene although yielded the bis-substituted crude product Zr(O i Pr) 2(OOCCHCl 2) 2(HO i Pr) ( 3) but its solution in toluene left for crystallization formed a tri-nuclear oxo product Zr 3(μ 3-O)(μ-O i Pr) 2(μ-OOCCHCl 2) 3(η-OOCCHCl 2) 2(O i Pr) 3 ( 3a). The three zirconium atoms in the structure of ( 3) are forming an isosceles triangle with a triply bridged oxo moiety at its center.