铈吡唑盐和吡咯盐取代基对二氧化碳活化的影响。
Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation.
机构信息
Institute of Inorganic Chemistry, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
出版信息
Molecules. 2021 Mar 31;26(7):1957. doi: 10.3390/molecules26071957.
Homoleptic ceric pyrazolates (pz) Ce(RR'pz) (R = R' = Bu; R = R' = Ph; R = Bu, R' = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe)] with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO insertion was found to increase in the order of Bupz < Phpz < BuMepz < Mepz. For comparison, the pyrrole-based ate complexes [Ce(pyr)(-pyr)(thf)][Li(thf)] (pyr = pyrrolato) and [Ce(cbz)(thf)][Li(thf)] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe)]Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO seemed promising, but any reversibility could not be observed.
偕金属铈吡唑配合物（pz）Ce(RR'pz)（R = R' = Bu；R = R' = Ph；R = Bu，R' = Me）是通过 Ce[N(SiHMe)] 与相应吡唑衍生物的质子解反应合成的。研究了所得配合物对 CO 的反应性，发现吡唑配体上取代基的体积对其影响显著。CO 插入的效率按 Bupz < Phpz < BuMepz < Mepz 的顺序增加。为了比较，通过质子解偕金属铈烷基金属配合物 Ce[N(SiHMe)]Li(thf)，分别用吡咯和咔唑获得了基于吡咯的双（吡咯烷酮）合金属配合物[Ce(pyr)(-pyr)(thf)][Li(thf)]（pyr = 吡咯烷酮）和[Ce(cbz)(thf)][Li(thf)]（cbz = 咔唑烷酮）。用 CO 处理吡咯烷酮/咔唑烷酮配合物似乎很有前景，但未观察到任何可逆性。
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