Un exemple de relaxation nucléaire controlée par un échange chimique: la solvatation du cation Mn2+ dans le diméthylsulfoxyde par RMN du proton

Advances in Molecular Relaxation Processes Pub Date : 1975-10-01 DOI:10.1016/0001-8716(75)80026-5

Jean-Claude Boubel, Jean-Jacques Delpuech

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引用次数: 6

Abstract

Proton relaxation times of dimethylsulfoxide containing 10⁻²–10⁻¹ M manganese (II) perchlorate are measured at two frequencies, 8 and 60 MHz, and sixteen temperatures (20–165 °C). These data allow us to compute: the contact shift Δω_M = 748 ± 13 Hz (25 °C and 60 MHz); the hyperfine coupling constant; the kinetic parameters for the exchange: bound DMSO

bulk DMSO: k_M = (6.3 ± 2.3) × 10⁶ s⁻¹; ΔH^≠ = 7.4 ± 0.5 kcal mol⁻¹; ΔS^≠ = −2.4 ± 0.5 u.e (25 °C), the rotational correlation time: τ_C = (9.65 ± 0.63) × 10⁻¹¹ s and the distance between protons and Mn²⁺ cation: r = 4.37 ± 0.05 Å (25 °C); the electronic relaxation time: 1/T_1e = (5.0 ± 1.0) × 10⁷ s⁻¹. These results describe the geometry and mobility of the first solvation shell and are compared with other examples from the literature.

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由化学交换控制的核松弛的一个例子:质子核磁共振在二甲基亚砜中溶解Mn2+阳离子

质子弛豫时间二甲亚砜含有10−2-10−1 M锰(II)高氯酸盐测量在两个频率，8和60 MHz，和16个温度(20-165℃)。这些数据使我们能够计算:接触位移ΔωM = 748±13 Hz(25°C和60 MHz);超细耦合常数;交换动力学参数:结合DMSO体DMSO: kM =(6.3±2.3)× 106 s−1;ΔH≠= 7.4±0.5 kcal mol−1;ΔS≠=−2.4±0.5 u.e(25℃)，旋转相关时间τC =(9.65±0.63)× 10−11 s，质子与Mn2+阳离子之间的距离r = 4.37±0.05 Å(25℃);电子弛豫时间:1/T1e =(5.0±1.0)× 107 s−1。这些结果描述了第一溶剂化壳的几何形状和迁移率，并与文献中的其他例子进行了比较。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Advances in Molecular Relaxation Processes

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