Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes.
Facile Access to NaOC≡As and Its Use as an Arsenic Source To Form Germylidenylarsinidene Complexes.
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DOI：
10.1002/anie.201703731
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发表时间：
2017-06
影响因子：
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通讯作者：
Shenglai Yao;Yves Grossheim;A. Kostenko;Ernesto Ballestero‐Martínez;Stefan Schutte;M. Bispinghoff;H. Grützmacher;M. Driess
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文献类型：
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作者：
Shenglai Yao;Yves Grossheim;A. Kostenko;Ernesto Ballestero‐Martínez;Stefan Schutte;M. Bispinghoff;H. Grützmacher;M. Driess
据报道，在 NaOt Bu 和 1,4-二恶烷存在下，通过砷化氢气体与碳酸二甲酯的反应，以 78% 的产率轻松一锅合成 [Na(OC≡As)(二恶烷)x ] (x=2.3-3.3)。它已被用于通过与 LGeCl (1) 反应合成第一个胂烯基官能化的亚甲甲亚甲基 [LGeAsCO] (2, L=CH[CMeN(Dipp)]2 ；Dipp=2,6-i Pr2 C6 H3 )。暴露在环境光下时，2 会发生 CO 消除，形成 1,3-digerma-2,4-二砷环丁二烯 [L2 Ge2 As2 ] (3)，其中包含具有叶立德状 Ge=As 键的对称 Ge2 As2 环。值得注意的是，位于 2 砷中心的 CO 配体可以与 PPh3 或 N-杂环卡宾 iPr NHC 供体 (iPr NHC=1,3-二异丙基-4,5-二甲基咪唑-2-亚基) 交换，得到新型甲亚基亚苋络合物 [LGe-AsPPh3 ] (4) 和 [LGe-As(iPr NHC)] (5) 分别证明了类砷亚烷基 As 原子上的类过渡金属配体取代。通过DFT计算研究了2-5的形成及其电子结构。
A facile, one-pot synthesis of [Na(OC≡As)(dioxane)x ] (x=2.3-3.3) in 78 % yield is reported through the reaction of arsine gas with dimethylcarbonate in the presence of NaOt Bu and 1,4-dioxane. It has been employed for the synthesis of the first arsaketenyl-functionalized germylene [LGeAsCO] (2, L=CH[CMeN(Dipp)]2 ; Dipp=2,6-i Pr2 C6 H3 ) from the reaction with LGeCl (1). Upon exposure to ambient light, 2 undergoes CO elimination to form the 1,3-digerma-2,4-diarsacyclobutadiene [L2 Ge2 As2 ] (3), which contains a symmetric Ge2 As2 ring with ylide-like Ge=As bonds. Remarkably, the CO ligand located at the arsenic center of 2 can be exchanged with PPh3 or an N-heterocyclic carbene iPr NHC donor (iPr NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) to afford the novel germylidenylarsinidene complexes [LGe-AsPPh3 ] (4) and [LGe-As(iPr NHC)] (5), respectively, demonstrating transition-metal-like ligand substitution at the arsinidene-like As atom. The formation of 2-5 and their electronic structures have been studied by DFT calculations.