Cyclopropanation and Isomerization Reactions of β-Diketiminato Boron Complexes
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The reaction of HC[(CBut)(NAr)]2Li with BCl3 yielded the azaallyl boron dichloride [ArNC(But)C(H)C(But)N(Ar)]BCl2 (1), which can be converted to the β-diketiminato boron dichloride HC[(CBut)(NAr)]2BCl2 (2) upon heating at 40 °C. Reaction of 1 with the bulky lithium salts LiN(SiMe3)2 and MesLi (Mes = 2,4,6-Me3C6H2) resulted in the cyclopropanation of the CBut group via the deprotonation of the methyl group, while reactions with PhLi and LiNEt2 gave substitution products.
HC[(CBut)(NAr)]₂Li(其中But为叔丁基、Ar为芳基)与三氯化硼(BCl₃)反应,得到氮杂烯丙基二氯化硼(azaallyl boron dichloride)[ArN=C(But)CHC(But)NAr]BCl₂(化合物1);该化合物在40℃加热条件下可转化为β-二亚胺基二氯化硼(β-diketiminato boron dichloride)HC[(CBut)(NAr)]₂BCl₂(化合物2)。化合物1与大位阻锂盐双(三甲基硅基)氨基锂(LiN(SiMe₃)₂)以及均三甲苯基锂(MesLi,其中Mes=2,4,6-三甲基苯基)发生反应时,通过甲基去质子化过程使CBut基团发生环丙烷化反应;而化合物1与苯基锂(PhLi)、二乙基氨基锂(LiNEt₂)反应则得到取代产物。



