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DOI: 10.1039/A903096D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3611-3615

Grafting of bulky rare earth metal complexes onto mesoporous silica MCM-41[hair space]†

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Reiner Anwander, Hans W. Görlitzer, Gisela Gerstberger, Clemens Palm, Oliver Runte and Michael Spiegler

Abstract

Heteroleptic yttrium bis(dimethylsilyl)amide complexes featuring chelating N,N[hair space]′-bis(3,5-di-tert-butylsalicylidene)ethane-1,2-diamine (H2L1) and trans-1,2-bis(2,4,6-triisopropylbenzenesulfonamido)cyclohexane (H2L2) ligands were immobilized on mesoporous silica MCM-41 according to a heterogeneously performed silylamide route. FTIR Spectroscopy revealed a novel grafting sequence involving amine elimination and subsequent metal siloxide formation and surface silylation. Nitrogen adsorption/desorption isotherms of the resulting hybrid materials obtained at 77.4 K indicated peculiarities of the immobilization process such as the presence of differently modified mesopores. According to preliminary catalytic investigations, the hybrid materials exhibit promising catalytic activity in a hetero Diels–Alder reaction (Danishefsky transformation). Molecular model complexes were synthesized via amine elimination reactions with triphenylsilanol and fully characterized by means of spectroscopy (FTIR, 1H, 13C, 29Si NMR). Mononuclear [YL1(OSiPh3)(thf[hair space])(CH3CN)] adopts a slightly distorted pentagonal bipyramidal geometry in the solid state, with the (planar) L1 and acetonitrile ligands located in the equatorial plane.

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