Reactions of group 4 metallocenes with monosubstituted acetonitriles: keteniminate formation versus C-C coupling.
Reactions of group 4 metallocenes with monosubstituted acetonitriles: keteniminate formation versus C-C coupling.
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DOI：
10.1002/chem.201406219
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发表时间：
2015-02
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影响因子：
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通讯作者：
Lisanne Becker;Martin Haehnel;A. Spannenberg;P. Arndt;U. Rosenthal
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文献类型：
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作者：
Lisanne Becker;Martin Haehnel;A. Spannenberg;P. Arndt;U. Rosenthal
在1a的情况下，第4族金属茂二氯化物[Cp '2 MCl 2]（1a：M=Ti，Cp'= Cp*=η（5）-五甲基吡啶，1 B：M=Zr，Cp '= Cp *=η（5）-三甲基吡啶）与锂化的MesCH 2-C H2 N反应得到[Cp*2 TiCl（N=C=C（HMes））]（3; Mes=均三甲苯基）。对于化合物1 B，腈-腈偶联导致4中的五元桥。茂金属炔配合物[Cp*2 Zr（η（2）-Me 3 SiC 2 SiMe 3）]（2）与PhCH 2-CN反应，第一步生成不稳定产物[Cp*2 Zr（η（2）-Me 3 SiC 2 SiMe 3）（NC= CH 2 Ph）]（5）。除去炔后，形成产物的混合物。通过改变溶剂和反应温度，分离出三种化合物：二氮杂二烯络合物6、双（烯酮亚胺）络合物7和具有烯酮亚胺配体和五元金属配体的8。随后的变化的Cp配体和金属中心，通过使用[Cp 2 Zr]和[Cp*2 Ti]与Me 3 SiC 2 SiMe 3在与PhCH 2-CN的反应中得到复杂的混合物。
The reactions of the Group 4 metallocene dichlorides [Cp'2 MCl2 ] (1 a: M=Ti, Cp'=Cp*=η(5) -pentamethylcyclopentadienyl, 1 b: M=Zr, Cp'=Cp=η(5) -cyclopentadienyl) with lithiated MesCH2-C≡N gave [Cp*2 TiCl(N=C=C(HMes))] (3; Mes=mesityl) in the case of 1 a. For compound 1 b, a nitrile-nitrile coupling resulted in a five-membered bridge in 4. The reaction of the metallocene alkyne complex [Cp*2 Zr(η(2) -Me3 SiC2 SiMe3 )] (2) with PhCH2 C≡N led in the first step to the unstable product [Cp*2 Zr(η(2) -Me3 SiC2 SiMe3 )(NC=CH2 Ph)] (5). After the elimination of the alkyne, a mixture of products was formed. By variation of the solvent and the reaction temperature, three compounds were isolated: a diazadiene complex 6, a bis(keteniminate) complex 7, and 8 with a keteniminate ligand and a five-membered metallacycle. Subsequent variation of the Cp ligand and the metal center by using [Cp2 Zr] and [Cp*2 Ti] with Me3 SiC2 SiMe3 in the reactions with PhCH2-C≡N gave complex mixtures.