过去的十年见证了卡宾稳定的低价硅化合物领域的巨大增长,揭示了这些分子非常令人兴奋的特性。在这里,我们使用了双环(烷基)(氨基)卡宾,(MeBICAAC)探索硅化合物的低价化学。双环(烷基)(氨基)卡宾-SiCl4络合物的还原,[(MeBICAAC)SiCl4](1)与KC8提供了低价Si配合物,包括Si(III)自由基[(MeBICAAC)SiCl3](2)和具有形式零价状态的硅中心的络合物,[(MeBICAAC)2Si](3)。同样,原位生成的Me2SiCl2与一当量KC8的MeBICAAC加合物的还原导致形成[(MeBICAAC)SiMe2Cl](4)具有未配对电子的络合物。这些配合物已经通过IR,UV-Vis。,NMR,HRMS,EPR及其固态结构也通过单晶X射线晶体学阐明。Further,DFT计算揭示了络合物1、3的较低能量单重态和络合物2、4的双重态。
Past one decade has witnessed a tremendous growth in the field of carbenes stabilized low-valent silicon compounds unravelling very exciting properties of these molecules. Herein, we have employed a bicyclic (alkyl)(amino)
carbene, (MeBICAAC) to explore the low-valent chemistry of silicon compounds. The reduction of bicyclic (alkyl)(amino)
carbene-SiCl4 complex, [(MeBICAAC)SiCl4] (1) with KC8 afforded low-valent Si complexes, including Si(III) radical [(MeBICAAC)SiCl3] (2) and a complex with silicon center in a formal zero-valent state, [(MeBICAAC)2Si] (3). Similarly, the reduction of in-situ generated MeBICAAC adduct of Me2SiCl2 with one equivalent of KC8 led to the formation of [(MeBICAAC)SiMe2Cl] (4) complex having an unpaired electron. These complexes have been characterized by IR, UV-Vis., NMR, HRMS, EPR and their solid-state structures were also elucidated by single crystal X-ray crystallography. Further, DFT calculations revealed the lower energy singlet state for complexes 1, 3 and doublet state for complexes 2, 4.