Transition metal complexes of cubic (T 8) oligo-silsesquioxanes

• Published in: Journal of molecular structure 2008-11, Vol.890 (1), p.232-239
• Main Authors: Goodgame, D.M.L., Kealey, S., Lickiss, P.D., White, A.J.P.
• Format: Article
• Language: English
• Subjects: Crystal structure; Octaimide; Silsesquioxane; Zn(II) complex
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2008.05.013

Acid hydrolysis of (EtO) 3Si(CH 2) 3NH 2 in the presence of ZnCl 2 affords the silsesquioxane derivative [Si 8O 12((CH 2) 3NH 3) 8] 8+·2.8[ZnCl 4] 2−·2.4[Cl] −, which has been characterized by X-ray crystallography. Direct reaction of [Si 8O 12((CH 2) 3NH 3) 8]Cl 8 with the chlorides of Co(II), Cu(II) and Cd(II) in methanol gave the compounds [Si 8O 12((CH 2) 3NH 3) 8][MCl 4] 4 (M = Co, Cu, Cd) but of insufficient crystal quality for X-ray study. The octaimide Si 8O 12[(CH 2) 3N(COMe) 2] 8 was obtained by reacting [Si 8O 12((CH 2) 3NH 3) 8]Cl 8 with acetic anhydride and X-ray crystallography shows it to have a slightly flattened structure rather than having the eight pendant groups pointing to the corners of a cube. Metal complexes of the silsesquioxane Si 8O 12((CH 2) 3NH 2) 8 (L) of stoichiometry L(MX 2) 2 with some salts of Ni, Cu, Zn, and Cd are also reported.