Gas-Phase Preparation of 1-Germavinylidene (H 2 CGe; X 1 A 1 ), the Isovalent Counterpart of Vinylidene (H 2 CC; X 1 A 1 ), via Non-adiabatic Dynamics through the Elementary Reaction of Ground State Atomic Carbon (C; 3 P) with Germane (GeH 4 ; X 1 A 1 )
Gas-Phase Preparation of 1-Germavinylidene (H 2 CGe; X 1 A 1 ), the Isovalent Counterpart of Vinylidene (H 2 CC; X 1 A 1 ), via Non-adiabatic Dynamics through the Elementary Reaction of Ground State Atomic Carbon (C; 3 P) with Germane (GeH 4 ; X 1 A 1 )
复制标题
通过基态原子碳的基本反应，通过非绝热动力学气相制备 1-Germavinylidene (H 2 CGe; X 1 A 1 )，其是亚乙烯基 (H 2 CC; X 1 A 1 ) 的等价对应物 (
DOI：
10.1021/acs.jpclett.2c03749
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Kaiser, Ralf I.
中科院分区：
文献类型：
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作者：
Yang, Zhenghai;Sun, Bing-Jian;He, Chao;Li, Jin-Qi;Chang, Agnes H.;Kaiser, Ralf I.
1-Germavinylidene (H2CGe; X1A1) 是亚乙烯基 (H2CC; X1A1) 的锗类似物，是通过基态原子碳 (C;3P) 与锗烷 (GeH4; X1A1) 在单次碰撞条件下的双分子反应直接气相合成制备的。该反应开始于碳无势垒地插入到 Ge-H 键中，然后从三重态表面到单重态表面进行系间跨越，原子氢迁移到亚甲锗烷基 (H2GeCH2)，后者主要通过分子氢损失分解为 1-甲亚乙烯基 (H2CGe; X1A1)。因此，用锗取代乙炔-亚乙烯基体系中的单个碳原子会严重影响卡宾型结构的化学键、分子结构和热力学稳定性，有利于1-亚乙烯基（H2CGe）而不是亚锗炔（HGeCH）160 kJ mol-1。因此，碳-锗烷系统代表了探索第14主族元素化学的基准，其中含锗系统与等价碳系统几乎没有相似之处。
1-Germavinylidene (H2CGe; X1A1), the germanium analogue of vinylidene (H2CC; X1A1), was prepared via a directed gas-phase synthesis through the bimolecular reaction of ground state atomic carbon (C;3P) with germane (GeH4; X1A1) under single-collision conditions. The reaction commences with the barrierless insertion of carbon into the Ge–H bond followed by intersystem crossing from the triplet to singlet surface and migration of atomic hydrogen to germylene (H2GeCH2), which predominantly decomposes via molecular hydrogen loss to 1-germavinylidene (H2CGe; X1A1). Therefore, the replacement of a single carbon atom in the acetylene–vinylidene system by germanium critically impacts the chemical bonding, molecular structure, and thermodynamic stability of the carbene-type structures favoring 1-germavinylidene (H2CGe) over germyne (HGeCH) by 160 kJ mol–1. Hence, the carbon–germane system represents a benchmark in the exploration of the chemistries of main group 14 elements with germanium-bearing systems showing few similarities with the isovalent carbon system.