Synthesis, Characterization, and Reactivity of Low-Coordinate Titanium(III) Amido Complexes
Synthesis, Characterization, and Reactivity of Low-Coordinate Titanium(III) Amido Complexes
复制标题
DOI：
10.1021/acs.organomet.2c00162
复制
发表时间：
2022-06-13
期刊：
影响因子：
2.8
通讯作者：
Tilley, T. Don
中科院分区：
文献类型：
--
作者：
De Lucio, Alejandro J. Cuellar;Cai, Irene C.;Tilley, T. Don
低配位的钛（III）酰胺基配合物通过用1或2当量的Li[N（SiiPr（3））DIPP]（DIPP = 2，6-二异丙基苯基）处理β-TiCl 3以分别形成双核[{Ti（N（SiiPr（3））DIPP）Cl（mu-Cl）}（2）]（1）或单核Ti[N（SiiPr（3））DIPP]（2）Cl（2）而容易地制备。这两种配合物的特征在于通过各种方法，包括NMR光谱，埃文斯法磁化率，和单晶X-射线衍射研究。配合物1被证明是用于盐复分解反应以形成带有烷氧基或甲硅烷基配体的混配配合物的通用前体。或者，1与刘易斯碱如4-二甲基氨基吡啶（DMAP）形成加合物，其为顺磁性单核物质。碱稳定的络合物5用1或2当量的LiCH 2SiMe 3烷基化以分别形成单烷基或二烷基产物。相比之下，在不存在DMAP的情况下用2当量的LiCH 2SiMe 3处理络合物1导致最终形成具有[Ti-2（μ-Cl）（2）（μ：eta（1）-CH 2SiMe 2CH 2-）]核的双核环化络合物9。本研究证明了一个家庭的低配位钛（III）酰胺配合物具有各种中性和单阴离子配体的方便的合成。
Low-coordinate titanium(III) amido complexes were readily prepared via treatment of beta-TiCl3 with 1 or 2 equiv of Li[N(SiiPr(3))DIPP] (DIPP = 2,6-di-iso-propylphenyl) to form dinuclear [{Ti(N(SiiPr(3))DIPP)Cl(mu-Cl)}(2)] (1) or mononuclear Ti[N(SiiPr(3))DIPP](2)Cl (2), respectively. Both complexes were characterized by a variety of methods, including NMR spectroscopy, Evans method magnetic susceptibility, and single-crystal X-ray diffraction studies. Complex 1 was shown to be a versatile precursor for salt metathesis reactions to form heteroleptic complexes bearing alkoxide or silyl ligands. Alternatively, 1 formed adducts with Lewis bases such as 4-dimethylaminopyridine (DMAP) that are paramagnetic, mononuclear species. The base-stabilized complex 5 was alkylated with 1 or 2 equiv of LiCH2SiMe3 to form mono- or dialkyl products, respectively. In contrast, treatment of complex 1 in the absence of DMAP with 2 equiv of LiCH2SiMe3 results in the ultimate formation of a dinuclear cyclometalated complex 9 bearing a [Ti-2(mu-Cl)(2)(mu:eta(1)-CH2SiMe2CH2-)] core. This study demonstrates the convenient synthesis of a family of low-coordinate titanium(III) amido complexes possessing a variety of neutral and monoanionic ligands.