Nitrile regio-synthesis by Ni centers on a siliceous surface: implications in prebiotic chemistry
Nitrile regio-synthesis by Ni centers on a siliceous surface: implications in prebiotic chemistry
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Ni在硅质表面上进行腈区域合成：对生命起源前化学的影响
DOI：
10.1039/d2cc04361k
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发表时间：
2022
影响因子：
4.9
通讯作者：
DeYonker, Nathan J.
中科院分区：
文献类型：
--
作者：
Fioroni, Marco;DeYonker, Nathan J.
通过量子化学（PBE 0/def 2-TZVPP; DLPNO-CCSD（T）/cc-pVTZ）和多面体低聚倍半硅氧烷（POSS）小而可靠的模型，从理论上探索了一系列与生命起源和生命化学起源相关的天体化学相关催化产物。在这项工作中，非均相氢氰化反应的不饱和CC键（丙烯）催化的Ni中心络合到二氧化硅表面进行了分析。在两种可能的区域异构体中，支链异丙基氰化物在动力学和热力学上优于直链正丙基氰化物（T = 200 K）。腈类化合物的形成具有区域选择性，对生命起源和生命化学有着深远的影响，并与地球化学和地球化学有着深刻的联系。
By means of quantum chemistry (PBE0/def2-TZVPP; DLPNO-CCSD(T)/cc-pVTZ) and small, but reliable models of Polyhedral Oligomeric Silsesquioxanes (POSS), an array of astrochemically-relevant catalysis products, related to prebiotic and origin of life chemistry, has been theoretically explored. In this work, the heterogeneous phase hydrocyanation reaction of an unsaturated CC bond (propene) catalyzed by a Ni center complexed to a silica surface is analyzed. Of the two possible regioisomers, the branched iso-propyl-cyanide is thermodynamically and kinetically preferred over the linear n-propyl-cyanide (T = 200 K). The formation of nitriles based on a regioselective process has profound implications on prebiotic and origin of life chemistry, as well as deep connections to terrestrial surface chemistry and geochemistry.