Helling Christoph, Wölper Christoph, Schulte Yannick, Cutsail George E, Schulz Stephan
Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide) , University of Duisburg-Essen , Universitätsstraße 5-7 , D-45117 Essen , Germany.
Max Planck Institute for Chemical Energy Conversion (CEC) , Stiftstraße 34-36 , D-45470 Mülheim an der Ruhr , Germany.
Inorg Chem. 2019 Aug 5;58(15):10323-10332. doi: 10.1021/acs.inorgchem.9b01519. Epub 2019 Jul 23.
A convenient synthetic route to Ga-stabilized pnictogen-centered radicals and gallapnictenes by manipulation of pnictogen-carbon bond strengths is presented. Two equivalents of LGa (L = HC[C(Me)N(Dip)], Dip = 2,6--PrCH) react with CpAsCl (Cp = C(4--BuCH)) with formation of the arsenic-centered radical [L(Cl)Ga]As·. In contrast, the analogous reaction with TerSbCl (Ter = 2,6-MesCH; Mes = 2,4,6-MeCH) yields the gallastibene LGa═SbTer () containing a Ga-Sb double bond, whereas reactions of DipSbCl with one and two equivalents of LGa give the monoinsertion and bisinsertion products L(Cl)GaSb(ClDip) () and [L(Cl]Ga]SbDip (), respectively. - were structurally characterized by single crystal X-ray diffraction. The description of as an arsenic-centered radical is consistent with results of electron paramagnetic resonance and density functional theory (DFT) studies. The π-bonding in LGa═SbTer () is estimated to 10.68 kcal mol by variable-temperature (VT) NMR spectroscopy, and DFT studies reveal a significant π-bonding interaction between Sb and Ga.
本文提出了一种通过控制氮族元素-碳键强度来合成镓稳定的以氮族元素为中心的自由基和镓氮族烯的便捷合成路线。两当量的LGa（L = HC[C(Me)N(Dip)]，Dip = 2,6-二异丙基苯基）与CpAsCl（Cp = C(4-叔丁基苯基)）反应，生成以砷为中心的自由基[L(Cl)Ga]As·。相比之下，与TerSbCl（Ter = 2,6-均三甲苯基；Mes = 2,4,6-三甲基苯基）的类似反应生成含有Ga-Sb双键的镓锑烯LGa═SbTer（），而DipSbCl与一当量和两当量的LGa反应分别得到单插入产物L(Cl)GaSb(ClDip)（）和双插入产物[L(Cl]Ga]SbDip（）。- 通过单晶X射线衍射对其结构进行了表征。将描述为以砷为中心的自由基与电子顺磁共振和密度泛函理论（DFT）研究结果一致。通过变温（VT）核磁共振光谱估计LGa═SbTer（）中的π键能为10.68 kcal mol，DFT研究表明Sb和Ga之间存在显著的π键相互作用。
