Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents.
Synthetic, structural and reaction chemistry of N-heterocyclic germylene and stannylene compounds featuring N-boryl substituents.
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DOI：
10.1039/c9dt02449b
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发表时间：
2019-08
影响因子：
4
通讯作者：
Lilja Kristinsdóttir;Nicola L Oldroyd;Rachel Grabiner;Alastair W. Knights;A. Heilmann;A. Protchenko;Haoyu Niu;E. Kolychev;Jesús Campos;Jamie Hicks;K. Christensen;S. Aldridge
中科院分区：
文献类型：
--
作者：
Lilja Kristinsdóttir;Nicola L Oldroyd;Rachel Grabiner;Alastair W. Knights;A. Heilmann;A. Protchenko;Haoyu Niu;E. Kolychev;Jesús Campos;Jamie Hicks;K. Christensen;S. Aldridge
本研究详细介绍了具有二氮杂硼杂环基基团{（HCDippN）2B}（Dipp = 2，6-iPr 2C 6 H3）的N-杂环甲锗烯和甲锡烯的合成，作为两个N-结合取代基，以期产生富电子和空间保护的金属中心。通过DFT计算探测了它们的关键前沿轨道--14族中心孤对轨道和正交pπ轨道（通常是HOMO-2和LUMO）的能量，并与相关的非环状类似物进行了比较，揭示了（在甲锡烯的情况下）与测量的119 Sn化学位移的相关性。锗烯系统对氧原子转移剂的反应性已被检查，与2：1的反应化学计量被观察到的Me 3 NO和吡啶N-氧化物，导致形成的产品被认为是从C-H键的活化衍生的瞬态第一形成的锗酮。
This study details the syntheses of N-heterocyclic germylenes and stannylenes featuring diazaborolyl groups, {(HCDippN)2B} (Dipp = 2,6-iPr2C6H3), as both of the N-bound substituents, with a view to generating electron rich and sterically protected metal centres. The energies of their key frontier orbitals - the group 14-centred lone pair and orthogonal pπ-orbital (typically the HOMO-2 and LUMO) have been probed by DFT calculations and compared with a related acyclic analogue, revealing (in the case of the stannylenes) a correlation with the measured 119Sn chemical shifts. The reactivity of the germylene systems towards oxygen atom transfer agents has been examined, with 2 : 1 reaction stoichiometries being observed for both Me3NO and pyridine N-oxide, leading to the formation of products thought to be derived from the activation of C-H bonds by a transient first-formed germanone.