One-Electron-Addition to Pentavalent Phosphorus with the Phosphorus-Chlorine Bond as Acceptor Introducing a Fundamental Distinction in Substitution Mechanism between S<sub>N</sub>2(P) and S<sub>N</sub>2(C)

• 作者: Henk M. Buck
• 来源期刊: 物理化学期刊(英文)
• 学科: 化学
• 关键词: Pentavalent PHOSPHORUS and Carbon Compounds σ*-Electron-Addition Single-Crystal Electron Spin Resonance (ESR) Model and Ab Initio Calculations Differences in SN2(C) vs. SN2(P) MECHANISM
• 年，卷（期）: wlhxqkyw_2019,（3）
• 页码范围: 182-191
• 页数: 10页
• 分类号: O6

摘要

An electron-addition, under single-crystal conditions, to pentavalent phosphorus compounds as Cl-P (=O, S) Y, Z with the P-Cl bond as electron-accepting group, is selected as an additional model for SN2(P) like reactions. It is demonstrated that the geometric information stored in the tetrahedral configuration (substrate) can be transmitted in the corresponding trigonal bipyramidal (TBP) state for nucleophilic substitution. In this article, we focus on these specific mechanistic aspects of carbon and phosphorus. We consider our study as a contribution to the significance of these (bio)chemical intermediates.