Groll Lisa, Kelly John A, Inoue Shigeyoshi
TUM School of Natural Sciences, Department of Chemistry, Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748, Garching, Germany.
Chem Asian J. 2024 Jan 15;19(2):e202300941. doi: 10.1002/asia.202300941. Epub 2023 Dec 7.
A heteroleptic amino(imino)stannylene (TMS N)(I BuN)Sn: (TMS=trimethylsilyl, I Bu=C[(N- Bu)CH] ) as well as two homoleptic NHI-stabilized tetrylenes, (I BuN) E: (NHI=N-heterocyclic imine, E=Ge, Sn) are presented. VT-NMR investigations of (I BuN) Sn: (2) reveal an equilibrium between the monomeric stannylene at room temperature and the dimeric form at -80 °C as well as in the solid state. Upon reaction of the homoleptic tetrylenes with CO , both compounds insert two equivalents of CO , however differing bonding modes can be observed. (I BuN) Sn: (2) inserts one equivalent of CO into each Sn-N bond, giving carbamato groups coordinated κ O,O' to the metal center. With (I BuN) Ge: (3), the Ge-N bonds stay intact upon activation, being bridged by one molecule of CO respectively, forming 4-membered rings. Furthermore, the reactivity of 2 towards N O was investigated, resulting in partial oxidation to form stannylene dimer [((I BuN) SnO)(I BuN)Sn:] (6).
本文报道了一种杂配氨基（亚氨基）亚锡烯（TMS N）（I BuN）Sn（TMS = 三甲基硅基，I Bu = C[(N - Bu)CH]）以及两种同配NHI稳定的四价元素化合物（I BuN）E（NHI = N - 杂环亚胺，E = Ge，Sn）。对（I BuN）Sn:（2）的变温核磁共振研究表明，在室温下单体亚锡烯与在 -80°C以及固态时的二聚体形式之间存在平衡。同配四价元素化合物与CO反应时，两种化合物都插入两当量的CO，但观察到不同的键合模式。（I BuN）Sn:（2）在每个Sn - N键中插入一当量的CO，生成以κ O,O' 配位到金属中心的氨基甲酸盐基团。对于（I BuN）Ge:（3），Ge - N键在活化时保持完整，分别由一分子CO桥连，形成四元环。此外，研究了2对N O的反应性，结果是部分氧化形成亚锡烯二聚体[((I BuN) SnO)(I BuN)Sn:]（6）。
