Matsumoto Rikiya, Nagata Koichi, Nakamura Ryo, Watanabe Takahito, Hashimoto Hisako
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki, Aoba-ku, Sendai 980-8578, Japan.
Molecules. 2024 Dec 18;29(24):5974. doi: 10.3390/molecules29245974.
Dihydrogen activation by metallogermylenes was investigated experimentally and theoretically. A neutral NHC-coordinated chlorometallogermylene was synthesized and converted to a cationic base-free metallogermylene of molybdenum via chloride abstraction. The cationic molybdogermylene showed enhanced reactivity toward H compared to the tungsten analog. The reaction mechanism was investigated by theoretical calculations, which revealed a novel route that proceeds via a new type of metal-ligand cooperative activation between the metal and divalent germanium moiety. The activation energy of this route is much lower than that of the alternative route via an "oxidative addition" type of reaction on the single Ge(II) center, which is generally proposed for organotetrylenes. The features of the frontier orbitals and the origin of the metal effect on the H activation are also described.
通过实验和理论研究了金属锗烯对氢气的活化作用。合成了一种中性NHC配位的氯代金属锗烯，并通过氯化物提取将其转化为钼的阳离子无碱金属锗烯。与钨类似物相比，阳离子钼锗烯对H表现出更高的反应活性。通过理论计算研究了反应机理，结果揭示了一条通过金属与二价锗部分之间新型金属-配体协同活化作用的新途径。该途径的活化能远低于通过在单个Ge(II)中心上进行“氧化加成”类型反应的替代途径的活化能，后者通常是有机四价体所提出的。还描述了前线轨道的特征以及金属对H活化作用的影响来源。
