Nguyen Minh Tho, Gusev Dmitry, Dmitrienko Anton, Gabidullin Bulat M, Spasyuk Denis, Pilkington Melanie, Nikonov Georgii I
Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario L2S 3A1, Canada.
Department of Chemistry and Biochemistry, Wilfrid Laurier University, 75 University Avenue West, Waterloo, Ontario N2L 3C5, Canada.
J Am Chem Soc. 2020 Mar 25;142(12):5852-5861. doi: 10.1021/jacs.0c01283. Epub 2020 Mar 11.
The germylone dimNHCGe (, dimNHC = diimino N-heterocyclic carbene) was successfully prepared via the reduction of the germanium cation [dimNHCGeCl] with KC. The molecular structure of was unambiguously established by both NMR spectroscopy and single-crystal X-ray diffraction. The reactivity of was investigated, revealing that it undergoes oxidative addition of HCl, CHI, and PhI, accompanied by an unusual migration of the H, Me, and Ph groups from germanium to the carbene ligand. Related chemistry was also observed with CFN, which results in the migration of the fluorinated pyridine moiety to the carbene ligand. Compound also undergoes cycloaddition with tetrachloro--benzoquinone to afford a Ge(IV) adduct.
通过用KC还原锗阳离子[dimNHCGeCl]成功制备了二亚氨基N-杂环卡宾锗（dimNHCGe，dimNHC =二亚氨基N-杂环卡宾）。通过核磁共振光谱和单晶X射线衍射明确确定了其分子结构。研究了其反应活性，发现它能发生HCl、CHI和PhI的氧化加成反应，同时伴随着H、Me和Ph基团从锗向卡宾配体的异常迁移。用CFN也观察到了相关化学现象，这导致氟化吡啶部分迁移到卡宾配体上。化合物还与四氯-对苯醌发生环加成反应，得到一种Ge(IV)加合物。
