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An Extremely Electron Poor Cationic Triazoliumylidene N-Heterocyclic Carbene: Experimental and Computational Studies
Organometallics ( IF 2.5 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.organomet.7b00670 Torsten Hölzel 1 , Maximilian Otto 1 , Hannes Buhl 1 , Christian Ganter 1
Organometallics ( IF 2.5 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.organomet.7b00670 Torsten Hölzel 1 , Maximilian Otto 1 , Hannes Buhl 1 , Christian Ganter 1
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The electronic properties of the long-known cationic 1,2,4-triazoliumylidene 3a have been determined. The 77Se NMR chemical shift of its Se adduct 9 (δ = 138 ppm) indicates that 3a is only moderately π-acidic. M(CO)2Cl complexes of 3a (M = Rh, Ir) allowed the IR spectroscopic determination of a TEP value of 2073 cm–1, the highest value known to date for a N-heterocyclic carbene (NHC). The properties of cationic 3a were compared to those of the related neutral triazolylidene 5, which was prepared for comparison. Density functional theory calculations support the experimental findings. Overall, the cationic carbene 3a has to be considered a very poor σ-donor. Nevertheless, 3a is able to form di- (19) and even tricationic bis-NHC complexes (20 and 21).
中文翻译：
极差电子阳离子的三唑亚烷基N-杂环碳烯：实验和计算研究
已经确定了众所周知的阳离子1,2,4-三唑鎓亚烷基3a的电子性质。硒加合物9的77 Se NMR化学位移（δ= 138 ppm）表明3a只是中等π酸性。M（CO）2 Cl配合物3a（M = Rh，Ir）使红外光谱法测定的TEP值为2073 cm –1，这是迄今为止N杂环卡宾（NHC）已知的最高值。将阳离子3a的性能与相关的中性三唑基亚砜5的性能进行了比较，已准备好进行比较。密度泛函理论计算支持了实验结果。总体而言，必须将阳离子卡宾3a视为非常差的σ供体。然而，3a能够形成di-（19）甚至三阳离子双-NHC络合物（20和21）。
更新日期：2017-11-08
中文翻译：
极差电子阳离子的三唑亚烷基N-杂环碳烯：实验和计算研究
已经确定了众所周知的阳离子1,2,4-三唑鎓亚烷基3a的电子性质。硒加合物9的77 Se NMR化学位移（δ= 138 ppm）表明3a只是中等π酸性。M（CO）2 Cl配合物3a（M = Rh，Ir）使红外光谱法测定的TEP值为2073 cm –1，这是迄今为止N杂环卡宾（NHC）已知的最高值。将阳离子3a的性能与相关的中性三唑基亚砜5的性能进行了比较，已准备好进行比较。密度泛函理论计算支持了实验结果。总体而言，必须将阳离子卡宾3a视为非常差的σ供体。然而，3a能够形成di-（19）甚至三阳离子双-NHC络合物（20和21）。
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