Molecular Ti^IV catecholates were obtained as dimeric complexes from protonolysis reactions of Ti(NMe₂)₄ with pyrocatechol (H₂CAT), 4‐tert‐butylcatechol (H₂CATtBu‐4), 3,5‐di‐tert‐butylcatechol (H₂CATtBu₂–3,5), 2,3‐dihydroxynaphthalene (H₂DHN) and 3,6‐di‐tert‐butylcatechol (H₂CATtBu₂–3,6). The heteroleptic monocatecholate amide complexes were characterized by X‐ray structure analysis but only [Ti(CAT)(NMe₂)₂]₂ and [Ti(DHN)(NMe₂)₂]₂ were obtained as pure compounds. The solid‐state structures revealed Ti^IV centers bridged by two catecholato ligands adopting a [κ²(O,µ‐O′)] coordination mode except for complex [Ti(CATtBu₂–3,6)(NMe₂)₂] featuring one bridging catecholato and one bridging amido ligand. Heteroleptic complex [Ti(DHN)(NMe₂)₂]₂ was grafted onto large‐pore periodic mesoporous silica KIT‐6 (convergent approach) and the resulting Ti^IV surface species compared with the established sequential approach, i.e., grafting of Ti(NMe₂)₄ onto the KIT‐6 material and subsequent ligand exchange with H₂DHN. Dimeric complex [Ti(DHN)(NMe₂)₂]₂ proved to be sufficiently reactive for a direct grafting yielding the same dominant surface species as obtained according to the sequential approach, as revealed by nitrogen physisorption, elemental analysis, and DRIFT/¹³C CP MAS spectroscopy.

中文翻译：

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邻苯二甲酸钛（IV）接枝的介孔二氧化硅KIT-6：探究顺序和会聚固定方法

分子的Ti ^IV儿茶酚分别得到的二聚复合物选自Ti（NME的质子分解反应₂）₄与邻苯二酚（H ₂ CAT），4-叔-butylcatechol（H ₂ CAT吨卜-4），3,5-二-叔-丁基儿茶酚（H ₂ CAT吨卜₂ -3,5-），2,3-二羟基萘（H ₂ DHN）和3,6-二-叔-butylcatechol（H ₂ CAT吨卜₂ -3,6-）。X射线结构分析表征了杂配单儿茶酚酰胺类配合物，但仅[Ti（CAT）（NMe ₂）₂ ] ₂和[Ti（DHN）（NMe ₂）₂ ] ₂为纯化合物。固态结构显示的Ti ^IV中心桥接由两个儿茶酚配体采用[κ ²（O，μ-O'）]，除了复杂的钛[Ti（CAT协调模式吨卜₂ -3,6-）（NME ₂）₂ ]以一种桥接儿茶酚和一种桥接酰胺配体为特征。将多杀菌剂[Ti（DHN）（NMe ₂）₂ ] ₂接枝到大孔周期性介孔二氧化硅KIT-6（会聚法）上，并生成Ti ^IV与已建立的顺序方法（即，将Ti（NMe ₂）₄接枝到KIT-6材料上，然后与H ₂ DHN进行配体交换）相比，发现了表面物种。二聚络合物[Ti（DHN）（NMe ₂）₂ ] ₂对于直接接枝具有足够的反应活性，可产生与按顺序方法获得的相同的主要表面物种，如氮物理吸附，元素分析和DRIFT / ^13所示。 C CP MAS光谱学。