Lanthanum alkoxides. Crystal structure of [La6(μ6-Cl)(μ3-OPri)2(μ-OPri)9(OPri)6]

• Published in: Russian journal of inorganic chemistry 2015-11, Vol.60 (11), p.1384-1389
• Main Authors: Suslova, E. V., Troyanov, S. I., Turova, N. Ya
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Physical Methods of Investigation
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023615110182

La(OR) 3 (R = Me, Et, Pr i , or C 2 H 4 OMe) has been synthesized via direct and electrochemical dissolution of metallic lanthanum in alcohols (in the presence of I 2 or a HgCl 2 /HgI 2 /Hg(OAc) 2 mixture catalysts or Bu 4 NBr or Et 3 BzNCl electrochemical additives, respectively). Lanthanum methoxide, ethoxide, and n -buthoxide have been synthesized via etherification of La(OPr i ) 3 and were characterized by IR spectroscopy and mass spectroscopy. The composition and physicochemical characteristics of lanthanum isopropoxide can vary over broad ranges depending on a method of its synthesis. The electrochemical dissolution of lanthanum in isopropanol or in the presence of I 2 catalytic amounts yields an insoluble polymeric product, and the synthesis of “La(OPr i ) 3 ” in the presence of a HgCl 2 /HgI 2 /Hg(OAc) 2 mixture results in the crystallization of La 6 Cl(OPr i ) 17 , whose composition and structure have been established by X-ray diffraction. In a La 6 (μ 6 -Cl)(μ 3 -OPr i ) 2 (μ-OPr i ) 9 (OPr i ) 6 molecule, lanthanum atoms form a trigonal prism centered by a chlorine atom (La–Cl, 3.14–3.15 Å), and isopropyl groups are μ 3 -bridging, μ 2 -bridging or terminal (La–O, 2.537, 2.435, and 2.152 Å, respectively).