School of Life and Environmental Sciences , Deakin University , Waurn Ponds , Australia , 3216.
J Org Chem. 2019 Sep 20;84(18):11813-11822. doi: 10.1021/acs.joc.9b01698. Epub 2019 Sep 3.
Siloxy carbenes, formed thermally or photochemically from acyl silanes via a 1,2-Brook rearrangement, are intriguing reactive intermediates that partake in a range of chemical reactions. To gain further insight into the properties of this class of carbenes, the thermodynamic stabilities of a series of known siloxy carbenes were explored on the basis of hydrogenation enthalpies. Calculations were conducted at the B3LYP-D3(BJ) level (using dispersion-corrected DFT) on siloxy carbenes (X-C-OSiR, singlet and triplet state), oxocarbenium ions (X-CH-OSiR), and their hydrogen addition products (X-CH-OSiR). Overall, strong correlation between singlet-triplet gaps and hydrogenation enthalpies was observed. Carbene stabilization enthalpy (CSE) values were also determined to provide additional insight into the structural features that influence the stability of siloxy carbenes.
硅氧卡宾，通过酰基硅烷的 1,2-Brook 重排热或光化学形成，是一种有趣的反应中间体，参与了一系列化学反应。为了更深入地了解这一类卡宾的性质，根据氢化焓探索了一系列已知硅氧卡宾的热力学稳定性。在 B3LYP-D3(BJ)水平（使用色散校正的 DFT）上对硅氧卡宾（X-C-OSiR，单重态和三重态）、氧杂卡宾离子（X-CH-OSiR）及其氢加成产物（X-CH-OSiR）进行了计算。总体而言，观察到单重态-三重态能隙与氢化焓之间存在很强的相关性。还确定了卡宾稳定化焓（CSE）值，以提供更多关于影响硅氧卡宾稳定性的结构特征的见解。
