Ancillary Tethering Influences σ 3 -P vs σ 5 -P Speciation and Enables Intermolecular S–H Oxidative Addition to Nontrigonal Phosphorus Compounds
Ancillary Tethering Influences σ 3 -P vs σ 5 -P Speciation and Enables Intermolecular S–H Oxidative Addition to Nontrigonal Phosphorus Compounds
复制标题
辅助束缚影响 α 3 -P 与 α 5 -P 形态并实现非三方磷化合物的分子间 S-H 氧化加成
DOI：
10.1021/acs.organomet.0c00750
复制
发表时间：
2021
期刊：
影响因子：
2.8
通讯作者：
Radosevich, Alexander T.
中科院分区：
文献类型：
--
作者：
Moon, Hye Won;Maity, Ayan;Radosevich, Alexander T.
描述了带有外围乙烯桥的非三角磷(III)三酰胺(2)的设计和合成。与缺乏乙烯桥的化合物 (1, (P{N[o-NMe-C6H4]2}))2 相比，E-H 加成 (E = OR, SR) 时仅形成 σ5-P 氧化加成产物，而不是通过一个 P-N 键协同加成形成 σ3-P 加合物。所得五配位正膦已通过多核核磁共振波谱和 X 射线晶体学进行了表征。对 σ3-P 和 σ5-P 物种相对能量的 DFT 计算表明，乙烯连接体通过限制沿 C-N 键的旋转，在能量上破坏了正膦产物 (2·[H][E]) 的 σ3-P 互变异构体的稳定性，有利于通过环链互变异构形成 σ5-P 正膦。
The design and synthesis of a nontrigonal phosphorus(III) triamide (2) bearing a peripheral ethylene bridge is described. By comparison to a compound lacking the ethylene bridge (1, (P{N[o-NMe-C6H4]2})),2is shown to exclusively form σ5-P oxidative addition products upon E–H addition (E = OR, SR) in preference to a σ3-P adduct from cooperative addition across one P–N bond. The resulting pentacoordinate phosphoranes have been characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations on relative energies of σ3-P and σ5-P species indicate that the ethylene linker in2energetically destabilizes the σ3-P tautomer of the phosphorane product (2·[H][E]) by constraining rotation along the C–N bond, favoring formation of σ5-P phosphoranes by ring–chain tautomerism.