Development and Application of New Method to Analyze NMR Parameters Separated by Factors to Control the Values, with Its Applications

2017 Fiscal Year Final Research Report

• Project/Area Number: 15K05425
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Wakayama University
• Principal Investigator: HAYASHI Satoko 和歌山大学, システム工学部, 准教授 (00294306)
• Co-Investigator(Kenkyū-buntansha): 中西 和郎 和歌山大学, 学内共同利用施設等, 名誉教授 (80110807)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Keywords: 量子化学計算 / NMR / 化学シフト / 結合定数 / 分子軌道法 / 相対論効果 / 構造

Outline of Final Research Achievements

Much attention has been paid to propose a new method to analyze NMR parameters separately by factors to control the values. NMR parameters were analyzed based on the contributions from occupied MOs (ψi) and transitions form ψi to vacant MOs (ψa), together with ψi to ψj, other occupied MOs. The nuclear spin-spin coupling constants were analyzed similarly.
Indirect one-bond nuclear spin-spin couplings between M and C (1J(M, C)) in Me4M, Me3M-, Ph4M, and Ph3M- (M = Pb, Sn, Ge, Si, and C) were analyzed considering the relativistic effect and employing the Slater-type basis sets. The contributions to 1JFC(M, C) (or 1JSD+FC(M, C)) were decomposed into those of occupied orbitals and occupied to unoccupied transitions. The s-type lone pair orbitals were demonstrated to contribute to the distinct relativistic effect on 1J(Pb, C) of Me3Pb- (and Ph3Pb-).
These results established firm basis to analyze NMR parameters separately by the factors.

Free Research Field

化学