Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert -Butoxy Halides, Cp x TiX y (O t Bu) 4–(x+y) ( x , y = 1, 2; X = Cl, Br)
Multicomponent Mechanochemical Synthesis of Cyclopentadienyl Titanium tert -Butoxy Halides, Cp x TiX y (O t Bu) 4–(x+y) ( x , y = 1, 2; X = Cl, Br)
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环戊二烯基钛叔丁氧基卤化物的多组分机械化学合成，Cp x TiX y (O t Bu) 4âª(x y) ( x , y = 1, 2; X = Cl, Br)
DOI：
10.1021/acsomega.8b00943
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发表时间：
2018
期刊：
影响因子：
4.1
通讯作者：
Hanusa, Timothy P.
中科院分区：
文献类型：
--
作者：
Boyde, Nicholas C.;Steelman, Grant W.;Hanusa, Timothy P.
用无溶剂研磨法制备式为CpxTiXy(OtBu)4-(x+y)(x，y=1，2；x=Cl，Br.)的叔丁氧基卤化钛.在氯衍生物的情况下，使用Cp2TiCl2作为起始原料；在溴化物的情况下，使用LiCp、TiBr4和Li[OtBu]的混合物。起始原料的化学计量比反映在反应的主要产物中。报道了Cp2TiCl(OtBu)、Cp2TiBr2(OtBu)和CpTiBr2(OtBu)的单晶X射线结构，以及Cp2TiCl(OIPR)和Cp2TiClOMe的重新测定。叔丁氧基衍生物以其近乎线性的Ti-O-C角(>；170°)而闻名，反映了Ti-Oπ键，这一解释得到了密度泛函理论计算的支持。
Titaniumtert-butoxy halides of the formula CpxTiXy(OtBu)4–(x+y)(x,y= 1, 2; X = Cl, Br) have been prepared thorough milling the reagents without solvent. In the case of the chloride derivatives, Cp2TiCl2is used as a starting material; in the case of the bromides, a mixture of LiCp, TiBr4, and Li[OtBu] is used. The stoichiometric ratios of the starting materials are reflected in the major products of the reactions. Single-crystal X-ray structures are reported for Cp2TiCl(OtBu), Cp2TiBr(OtBu), and CpTiBr2(OtBu), as well as for Cp2TiCl(OiPr) and a redetermination of Cp2TiCl(OMe). Thetert-butoxy derivatives are notable for their nearly linear Ti–O–C angles (>170°) that reflect Ti–O π-bonding, an interpretation supported with density functional theory calculations.