Synthesis and Structural Characterization of Lithium and Titanium Complexes Bearing a Bulky Aryloxide Ligand Based on a Rigid Fused-Ring s-Hydrindacene Skeleton

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• 作者：Shoya Kanazawa ; Taishi Ohira ; Shun Goda ; Naoki Hayakawa ; Tomoharu Tanikawa ; Daisuke Hashizume ; Yutaka Ishida ; Hiroyuki Kawaguchi ; Tsukasa Matsuo
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 5, 2016
• 年：2016
• 卷：55
• 期：13
• 页码：6643-6652
• 全文大小：608K
• 年卷期：0
• ISSN：1520-510X

文摘

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 ⁿBuLi 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]₂TiCl₂ (5a). We also isolated a trace amount of the tris(aryloxide) Ti(IV) complex, [(EMind)O]₃TiCl (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]₂TiCl(THF)₂ (8a). The discrete monomeric structures of the titanium complexes 4a, 5a, 6a, 7a, and 8a were determined by X-ray crystallography.