Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Dalton Trans. 2012 Jun 28;41(24):7319-26. doi: 10.1039/c2dt30219e. Epub 2012 May 11.
Magnesium silylamide complexes MgN(SiHMe(2))(2)(THF)(2) and MgN(SiPhMe(2))(2) were synthesized according to transsilylamination and alkane elimination protocols, respectively, utilizing MgN(SiMe(3))(2)(THF)(2) and Mg(n-Bu) as precursors. Cage-like periodic mesoporous silica SBA-1 was treated with donor solvent-free dimeric Mg{N(SiHMe(2))(2)}(2), Mg{N(SiMe(3))(2)}(2) and monomeric MgN(SiPhMe(2))(2), producing hybrid materials [Mg(NR(2))(2)]@SBA-1 with magnesium located mainly at the external surface. Consecutive grafting of Mg{N(SiHMe(2))(2)}(2) and Fe(II){N(SiHMe(2))(2)}(2) onto SBA-1 led to heterobimetallic hybrid materials which exhibit complete consumption of the isolated surface silanol groups, evidencing intra-cage surface functionalization. All materials were characterized by DRIFT spectroscopy, nitrogen physisorption and elemental analysis.
根据反式硅烷化和烷烃消除反应分别合成了镁硅酰胺配合物 MgN(SiHMe(2))(2)(THF)(2) 和 MgN(SiPhMe(2))(2)，使用 MgN(SiMe(3))(2)(THF)(2) 和 Mg(n-Bu) 作为前体。笼状介孔硅 SBA-1 用无供体溶剂的二聚体Mg{N(SiHMe(2))(2)}(2)、Mg{N(SiMe(3))(2)}(2)和单体 MgN(SiPhMe(2))(2)处理，生成主要位于外表面的镁定位的杂化材料[Mg(NR(2))(2)]@SBA-1。SBA-1 上连续接枝Mg{N(SiHMe(2))(2)}(2)和Fe(II){N(SiHMe(2))(2)}(2)得到杂双金属杂化材料，证明了笼内表面功能化，其孤立的表面硅醇基团完全消耗。所有材料均通过 DRIFT 光谱、氮气物理吸附和元素分析进行了表征。
