Soluble Alumotitanosilicates and Their Zirconium and Hafnium Analogues

• Published in: European Journal of Inorganic Chemistry 2011-11, Vol.2011 (31), p.4795-4799
• Main Authors: Huerta-Lavorie, Raúl, Rascón-Cruz, Fernando, Solis-Ibarra, Diego, Zavala-Segovia, Nieves, Jancik, Vojtech
• Format: Article
• Language: English
• Subjects: Aluminum; Silicates; Titanium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201100805

The synthesis of molecular heterometallic alumosilicates in good yields has been achieved by reaction between LAl(OH·thf)(μ‐O)Si(OH)(OtBu)2 (1, L = [HC{C(Me)N(Ar)}2]–, Ar = 2,6‐iPr2C6H3) and group 4 amides. These reactions lead to inorganic cycles (type I) and spirocycles (type II) containing six‐membered rings with unprecedented inorganic cores (O–Al–O–Si–O)nM (n = 1, 2; M = Ti, Zr and Hf). Noteworthy, for the heavier metals, Zr and Hf, higher steric bulk in the alkyl substituent of the amide moiety is required to obtain type I compounds. The solid‐state structures for all compounds were determined and reveal a tetrahedral environment for all metal atoms, dihedral angles close to 90° for spirocyclic compounds, and isomorphous structures for the Zr and Hf derivatives. Unprecedented molecular heterobimetallic alumosilicates with inorganic cores O–Al–O–Si–O–M or (O–Al–O–Si–O)2M (M = Ti, Zr, Hf) have been prepared by reaction of the molecular alumosilicate LAl(OH)(μ‐O)Si(OH)(OtBu)2 (L = [HC{C(Me)N(Ar)}2]–, Ar = 2,6‐iPr2C6H3) with group 4 metal amides in different ratios.