1,2-C−H Activation of Benzene Promoted by (Arylimido)vanadium(V)-Alkylidene Complexes: Isolation of the Alkylidene, Benzyne Complexes
1,2-C−H Activation of Benzene Promoted by (Arylimido)vanadium(V)-Alkylidene Complexes: Isolation of the Alkylidene, Benzyne Complexes
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DOI：
10.1021/om200086n
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发表时间：
2011-02
期刊：
影响因子：
2.8
通讯作者：
Shu Zhang;M. Tamm;K. Nomura
中科院分区：
文献类型：
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作者：
Shu Zhang;M. Tamm;K. Nomura
的反应含咪唑啉-2-亚氨基配体的（芳基亚氨基）钒（V）二烷基配合物，V（NAr）（CH2SiMe3）2（L）[2，Ar = 2，6-Me2C6H3; L = ImDIPPN = 1，3-（2′，6 ′-二异丙基苯基）咪唑啉-2-亚氨基]，与C6 D 6或C6 H6发生反应，得到苯基络合物V（NAr）（CH 2 SiMe 3）（C6 H 5）（L）（3）或V（NAr）[CH（D）SiMe 3]（C6 D 5）（L）（3-d 6）通过经由钒（V）-亚烷基中间体的苯的1，2-C-H或C-D活化。2在正己烷中与PMe_3反应，得到钒（V）亚烷基配合物V（CHSiMe_3）（NAr）（ImDIPPN）（PMe_3）（4），并用X射线单晶衍射法测定了4的结构。3或3-d 6与C6 D 6或C6 H6反应，得到二苯基配合物V（NAr）（C6 H5）2（L）（5）或V（NAr）（C6 D5）2（L）（5-d10）。在PMe_3存在下进行同样的反应，得到了一个新的中间体，PMe_3捕获的苯炔配合物V（NAr）（η_2-C_6D_4）（L）（PMe_3）（6），并通过X射线衍射分析确定了6的结构。
Reactions of the (arylimido)vanadium(V) dialkyl complex containing an imidazolin-2-iminato ligand, V(NAr)(CH2SiMe3)2(L) [2, Ar = 2,6-Me2C6H3; L = ImDIPPN = 1,3-(2′,6′-diisopropylphenyl)imidazolin-2-iminato], with C6D6 or C6H6 took place affording the phenyl complex V(NAr)(CH2SiMe3)(C6H5)(L) (3) or V(NAr)[CH(D)SiMe3](C6D5)(L) (3-d6) by 1,2-C−H or C−D activation of benzene via a vanadium(V)-alkylidene intermediate. The reaction of 2 in n-hexane in the presence of PMe3 afforded the vanadium(V)alkylidene complex V(CHSiMe3)(NAr)(ImDIPPN)(PMe3) (4), and the structure of 4 has been determined by X-ray crystallography. The reaction of 3 or 3-d6 with C6D6 or C6H6 took place to afford the diphenyl complex V(NAr)(C6H5)2(L) (5) or V(NAr)(C6D5)2(L) (5-d10). The same reaction in the presence of PMe3 afforded the proposed intermediate, the PMe3-trapped benzyne complex V(NAr)(η2-C6D4)(L)(PMe3) (6), and the structure of 6 has been determined by X-ray diffraction analysis.