Isolable dicarbon stabilized by a single phosphine ligand
Isolable dicarbon stabilized by a single phosphine ligand
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由单一膦配体稳定的可分离二碳
DOI：
10.1038/s41557-020-00579-w
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发表时间：
2020-11-30
期刊：
影响因子：
21.8
通讯作者：
Frenking, Gernot
中科院分区：
文献类型：
--
作者：
Leung, Tsz-Fai;Jiang, Dandan;Frenking, Gernot
与天然存在的F2、O2和N2相比，双原子C2是一种有趣的物种，仅在气相中间接观察到，并且由于其高反应性而无法在凝聚相中分离。它以前在L→C2 <$L化合物中是稳定的，但在这个基序中中心C2的成键情况与游离C2的成键情况显著不同。在这里，我们制备和结构表征了双原子C2作为单配位的配合物L→ C2，使用带有两个咪唑烷-2-亚氨基的大体积膦配体（L是（NHCR=N）2（CH 3）P，其中NHCR是一个N-杂环卡宾）。该化合物在环境温度下在溶液中是稳定的，并且也以固态分离。反应性研究结合量子化学分析表明，L→ C2配合物的两个碳原子都具有卡宾性质。该配合物在热分解时发生了分子间C-H键活化，并表现出与甲醇类似的氢烷氧基化反应活性。
In contrast to naturally occurring F2, O2and N2, diatomic C2is an intriguing species that has only been observed indirectly in the gas phase, and because of its high reactivity has eluded isolation in the condensed phase. It has previously been stabilized in L→C2←L compounds but the bonding situation of the central C2in this motif differs remarkably from that of free C2. Here we have prepared and structurally characterized diatomic C2as a monoligated complex L→C2using a bulky phosphine ligand bearing two imidazolidin-2-iminato groups (L is (NHCR=N)2(CH3)P, where NHCRis an N-heterocyclic carbene). The compound is stable in solution at ambient temperature and has also been isolated in the solid state. Reactivity studies, in combination with quantum chemical analysis, suggest that the two carbon atoms of the L→C2complex both have carbene character. The complex underwent intermolecular C–H bond activation upon thermolysis and exhibited hydroalkoxylation-like reactivity with methanol.