Synthesis and Systematic Structural Analysis of Cationic Half‐Sandwich Ruthenium Chalcogenocarbonyl Complexes
Synthesis and Systematic Structural Analysis of Cationic Half‐Sandwich Ruthenium Chalcogenocarbonyl Complexes
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阳离子半夹心钌硫属羰基配合物的合成及系统结构分析
DOI：
10.1002/chem.201904600
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Saito Shinichi
中科院分区：
文献类型：
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作者：
Suzuki Ayumi;Mutoh Yuichiro;Tsuchida Noriko;Fung Chi‐Wai;Kikkawa Shoko;Azumaya Isao;Saito Shinichi
虽然过渡金属与羰基（CO）和硫代羰基（CS）配体的配合物的化学已经得到了很好的发展，但它们更重的类似物，即硒羰基（CSe）和碲羰基（CTe）配合物仍然很少。这种CSe和CTe络合物的有限可用性迄今阻碍了我们对这种硫族羰基（CE：E=O、S、Se、Te）配体之间的差异的理解。在此，我们报告了一系列阳离子半夹心钌CE配合物的合成和性质[CpRu（CE）（H2 IMes）（CNCH 2 Ts）][BArF 4]（Cp=η5-C5 H5-; H2 IMes = 1，3-二均三甲苯基咪唑啉-2-亚基; ArF= 3，5-（CF 3）2C 6 H3）。X射线衍射分析、NMR光谱分析和DFT计算的组合揭示了CE配体的π接受能力以O<S<Se<Te的顺序增加。由此获得的手性-at-金属CE络合物的变温NMR分析表明高立体化学稳定性。
Although the chemistry of transition‐metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half‐sandwich ruthenium CE complexes of the type [CpRu(CE)(H2IMes)(CNCH2Ts)][BArF4] (Cp=η5‐C5H5−; H2IMes=1,3‐dimesitylimidazolin‐2‐ylidene; ArF=3,5‐(CF3)2C6H3). A combination of X‐ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π‐accepting ability of the CE ligands in the order O<S<Se<Te. A variable‐temperature NMR analysis of the thus obtained chiral‐at‐metal CE complexes indicated high stereochemical stability.