Yerushalmi Roie, Baldridge Kim K, Scherz Avigdor
Department of Plant Sciences, The Weizmann Institute of Science, 76100 Rehovot, Israel.
J Am Chem Soc. 2003 Oct 22;125(42):12706-7. doi: 10.1021/ja035946y.
The prediction and measurement of charge distribution among interacting chemical entities in complex environments is a major challenge for modern chemistry. It encompasses information concerning fundamental quantities such as the electronic chemical potential and hardness of molecular fragments as well as their interactions with the surroundings. Although a wealth of theoretical work has been accumulated from the days of Pauling to the present, a specific molecular model system that allows quantitative and direct measurement of these properties has not yet been reported. Because atomic charges are not quantum mechanical observables, they cannot be derived from first principles, but rather they rely on the availability of high-precision experimental data and the interpretation of related experimental observables. Here, we demonstrate, for the first time, that a fragmental charge flow between a chelated metal center and reversibly bound molecules can be accurately monitored experimentally.
预测和测量复杂环境中相互作用的化学实体之间的电荷分布是现代化学面临的一项重大挑战。它涵盖了有关基本量的信息，如分子片段的电子化学势和硬度，以及它们与周围环境的相互作用。尽管从鲍林时代至今已经积累了大量的理论工作，但尚未报道过一种能够定量和直接测量这些性质的特定分子模型系统。由于原子电荷不是量子力学可观测量，它们不能从第一原理推导出来，而是依赖于高精度实验数据的可用性以及对相关实验可观测量的解释。在这里，我们首次证明，螯合金属中心与可逆结合分子之间的片段电荷流动可以通过实验准确监测。
