Olaru Marian, Duvinage Daniel, Lork Enno, Mebs Stefan, Beckmann Jens
Institut für Anorganische Chemie und Kristallographie, Universität Bremen, Leobener Straße 7, 28359, Bremen, Germany.
Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2018 Aug 6;57(32):10080-10084. doi: 10.1002/anie.201803160. Epub 2018 May 9.
Kinetically stabilized congeners of carbenes, R C, possessing six valence electrons (four bonding electrons and two non-bonding electrons) have been restricted to Group 14 elements, R E (E=Si, Ge, Sn, Pb; R=alkyl or aryl) whereas isoelectronic Group 15 cations, divalent species of type [R E] (E=P, As, Sb, Bi; R=alkyl or aryl), were unknown. Herein, we report the first two examples, namely the bismuthenium ion [(2,6-Mes C H ) Bi][BAr ] (1; Mes=2,4,6-Me C H , Ar =3,5-(CF ) C H ) and the stibenium ion [(2,6-Mes C H ) Sb][B(C F ) ] (2), which were obtained by using a combination of bulky meta-terphenyl substituents and weakly coordinating anions.
具有六个价电子（四个成键电子和两个非键电子）的动力学稳定的卡宾同系物R C，一直局限于第14族元素R E（E = Si、Ge、Sn、Pb；R = 烷基或芳基），而异电子的第15族阳离子，即[R E]类型的二价物种（E = P、As、Sb、Bi；R = 烷基或芳基），此前并不为人所知。在此，我们报告了前两个实例，即铋钌离子[(2,6-Mes₂CH)₂Bi][BArF₂₄]（1；Mes = 2,4,6-Me₃C₆H₂，ArF₂₄ = 3,5-(CF₃)₂C₆H₃）和锍离子[(2,6-Mes₂CH)₂Sb][B(C₆F₅)₄]（2），它们是通过使用庞大的间三联苯取代基和弱配位阴离子的组合而获得的。
