Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring s-Hydrindacene Skeleton
Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring s-Hydrindacene Skeleton
复制标题
DOI：
10.1021/acs.inorgchem.6b00762
复制
发表时间：
2016-07-04
影响因子：
4.6
通讯作者：
Matsuo, Tsukasa
中科院分区：
文献类型：
--
作者：
Kanazawa, Shoya;Ohira, Taishi;Matsuo, Tsukasa
基于刚性稠环1,1,3,3,5,5,7,7-octa-R-取代的s-茚苯骨架的大芳基醇，(Rind)OH (1) [Rind = EMind (a) 和 Eind (b)]，通过 (Rind)Li 与硝基苯反应并质子化来制备。用 (BuLi)-Bu-n 处理 1 得到芳氧基锂二聚体 [(Rind)OLi(THF)](2) (2) 或三聚体 [(Rind)OLi](3) (3)，具体取决于所使用的溶剂 (THF = 四氢呋喃)。 [(EMind)OLi(THF)](2) (2a) 与 TiCl4(THF)(2) 发生盐复分解反应，形成单核抗磁性单和双（芳氧基）Ti(IV) 配合物，[(EMind)O]TiCl3(THF) (4a) 和 [(EMind)O](2)TiCl2 (5a)。我们还分离出痕量的三（芳氧基）Ti(IV) 络合物，[(EMind)O](3)TiCl (6a)。 2a 和 TiCl3(THF)(3) 之间的反应导致单核顺磁单和双（芳氧基）Ti(III) 配合物的分离，[(EMind)O]TiCl2(THF)(2) (7a) 和 [(EMind)O](2)TiCl(THF)(2) (8a)。通过X射线晶体学测定钛络合物4a、5a、6a、7a和8a的离散单体结构。
The bulky aryl alcohols, (Rind)OH (1) [Rind = EMind (a) and Eind (b)], based on the rigid fused-ring 1,1,3,3,5,5,7,7-octa-R-substituted s-hydrindacene skeleton were prepared by the reaction of (Rind)Li with nitrobenzene followed by protonation. The treatment of 1 with (BuLi)-Bu-n affords the lithium aryloxide dimers [(Rind)OLi(THF)](2) (2) or trimers [(Rind)OLi](3) (3), depending on the employed solvents (THF = tetrahydrofuran). The salt metathesis reaction of [(EMind)OLi(THF)](2) (2a) with TiCl4(THF)(2) leads to the formation of the mononuclear diamagnetic mono- and bis(aryloxide) Ti(IV) complexes, [(EMind)O]TiCl3(THF) (4a) and [(EMind)O](2)TiCl2 (5a). We also isolated a trace amount of the tris(aryloxide) Ti(IV) complex, [(EMind)O](3)TiCl (6a). The reaction between 2a and TiCl3(THF)(3) resulted in the isolation of the mononuclear paramagnetic mono- and bis(aryloxide) Ti(III) complexes, [(EMind)O]TiCl2(THF)(2) (7a) and [(EMind)O](2)TiCl(THF)(2) (8a). The discrete monomeric structures of the titanium complexes 4a, 5a, 6a, 7a, and 8a were determined by X-ray crystallography.