Veroneau Samuel S, Mohar Jacob S, Bhunia Mrinal, Farber Hannah, Laughlin Alexander L, Voland Robert W, Bacon Alexandra, Gau Michael R, Lancaster Kyle M, Mindiola Daniel J
Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA, 19104, USA.
Department of Chemistry and Chemical Biology, Cornell University, 259 E Ave, Ithaca, NY, 14850, USA.
Angew Chem Int Ed Engl. 2025 Sep 26;64(40):e202511532. doi: 10.1002/anie.202511532. Epub 2025 Aug 25.
Carbon dioxide capture and functionalization sequesters carbon dioxide in more robust products and offers a viable route to reducing greenhouse gas emissions. We present herein a unique molecular Ti oxo anion that reversibly binds CO to allow both its sequestration and functionalization. The reduction of [(PN)Ti═O] (1) [PN = (2-PPr-4-methylphenyl)(mesityl)amide] with KC and 2.2.2-cryptand (crypt) resulted in formation of [K(crypt)][(PN)Ti═O] (2), which was fully characterized and shown to contain a Ti-centered radical. Complex 2 reacts with Al(CH) to form [K(crypt)][(PN)Ti{O(Al(CH)}] (3), which can be independently prepared from [K(crypt)][(PN)Ti(OCP)] and Al(CH). Whereas 1 does not react with CO, 2 rapidly captures the gas (1 atm, 25 °C) to produce a Ti carbonate [K(crypt)][(PN)Ti(κ-OC═O)] (4). Chemical and electrochemical oxidation of 4 releases CO to regenerate 1 while a soluble organic carbonate [MeSiOC(O)OSiMe, Me = CH] is obtained from reaction of 4 with ClSiMe.
二氧化碳捕获与官能团化将二氧化碳封存在更稳定的产物中，并提供了一条减少温室气体排放的可行途径。我们在此展示了一种独特的分子态钛氧阴离子，它能可逆地结合一氧化碳，从而实现其封存与官能团化。用 KC 和 2.2.2 - 穴醚（穴状配体）还原[(PN)Ti═O] (1) [PN = (2 - PPr - 4 - 甲基苯基)(均三甲苯基)酰胺]，得到了[K(穴状配体)][(PN)Ti═O] (2)，对其进行了全面表征，结果表明其含有一个以钛为中心的自由基。配合物 2 与 Al(CH)反应形成[K(穴状配体)][(PN)Ti{O(Al(CH)}] (3)，该配合物也可由[K(穴状配体)][(PN)Ti(OCP)]和 Al(CH)独立制备。虽然 1 不与一氧化碳反应，但 2 能迅速捕获该气体（1 个大气压，25°C），生成碳酸钛[K(穴状配体)][(PN)Ti(κ - OC═O)] (4)。对 4 进行化学和电化学氧化会释放出一氧化碳，使 1 再生，同时 4 与 ClSiMe 反应可得到一种可溶性有机碳酸盐[MeSiOC(O)OSiMe，Me = CH]。
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