Synthesis and grafting of CAN-derived tetravalent cerium alkoxide silylamide precursors onto mesoporous silica MCM-41

The heteroleptic tetravalent cerium complex [Ce(OiPr)(3){N(SiMe3)(2)}](2) was synthesised by treating ceric ammonium nitrate (CAN) sequentially with sodium isopropoxide and lithium bis(trimethylsilyl) amide in THF. The trivalent ate complex [Ce(OiPr)(2){N(SiMe3)(2)](2)}][Li(thf)(2)] was also isolated from these reaction mixtures. A transsilylamination reaction of [Ce(OiPr) (3){N(SiMe3)(2)}](2) with tetramethyldisilazane produced a considerable amount of homoleptic Ce[N(SiHMe2)(2)](4). The polymeric complex [Li2Ce2(OiPr)(10)(1,4-dioxane)](n) was isolated as an additional ligand redistribution product. When tetravalent complexes Ce[N(SiHMe2)(2)](4), Ce[N(SiMe3)(2)](3)Cl and Cp3CeCl were allowed to react with samples of periodic mesoporous silica MCM-41, Ce(IV) hybrid materials were produced. All hybrid materials were characterised via N-2 physisorption, elemental analysis and DRIFT spectroscopy.