Ruppert Heiko, Greb Lutz
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Department of Chemistry and Biochemistry - Inorganic Chemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2022 Mar 21;61(13):e202116615. doi: 10.1002/anie.202116615. Epub 2022 Feb 7.
Anionic, metal-centered nucleophiles are emerging compounds with unique reactivities. Here, we describe the isolation and full characterization of the first tetraamido tin(II) dianion, its behavior as ligand towards transition metals, and its reactivity as a tin-centered nucleophile. Experimental values such as the Tolman electronic parameter (TEP) and computations attest tin-located σ-donor ability exceeding that of carbenes or electron-rich phosphines. Against transition metals, the stannate(II) can act as η - or η -type ligand. With aldehydes, it reacts by hydride substitution to give valuable acyl stannates. The reductive dehalogenation of iodobenzene indicates facile redox pathways mediated by halogen bond interaction. Calix[4]pyrrolato stannate(II) represents the first example of this macrocyclic ligand in low-valent p-block element chemistry.
以金属为中心的阴离子亲核试剂是一类具有独特反应活性的新兴化合物。在此，我们描述了首个四酰胺基锡（II）二价阴离子的分离与全面表征、其作为过渡金属配体的行为以及作为以锡为中心的亲核试剂的反应活性。诸如托尔曼电子参数（TEP）等实验值以及计算结果证明，锡的σ供体能力超过了卡宾或富电子膦。对于过渡金属，锡酸盐（II）可作为η或η型配体。与醛类反应时，它通过氢化物取代反应生成有价值的酰基锡酸盐。碘苯的还原脱卤反应表明，卤素键相互作用介导了 facile 氧化还原途径。杯[4]吡咯锡酸盐（II）代表了这种大环配体在低价p区元素化学中的首个实例。
