Density Functional Theory Study on Aqueous Aluminum-Fluoride Complexes: Exploration of the Intrinsic Relationship between Water-Exchange Rate Constants and Structural Parameters for Monomer Aluminum Complexes

XIAOYAN JIN; ZHAOSHENG QIAN; BANGMEI LU; WENJING YANG; SHUPING   BI

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Density Functional Theory Study on Aqueous Aluminum-Fluoride Complexes: Exploration of the Intrinsic Relationship between Water-Exchange Rate Constants and Structural Parameters for Monomer Aluminum Complexes

机译：水性铝氟络合物的密度泛函理论研究：单体铝络合物的水交换速率常数与结构参数之间的内在联系的探讨

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Density functional theory (DFT) calculation is carried out to investigate the structures, ~(19)F and ~(27)Al NMR chemical shifts of aqueous Al-F complexes and their water-exchange reactions. The following investigations are performed in this paper: (1) the microscopic properties of typical aqueous Al-F complexes are obtained at the level of B3LYP/6-311+G**. Al—OH_2 bond lengths increase with F~ replacing inner-sphere H_20 progressively, indicating labilizing effect of F~ ligand. The AI-0H_2 distance trans to fluoride is longer than other Al—0H_2 distance, accounting for trans effect of F~ ligand. 19F and ~(27)AI NMR chemical shifts are calculated using GIAO method at the HF/6-311+G** level relative to RH_20)_6-and AI(H_20)6~(3+) references, respectively.The results are consistent with available experimental values; {2) the dissociative (D) activated mechanism is observed by modeling water-exchange reaction for [AI(H_20)6-iFi]l3-'1+ (/ = 1-4). The activation energy barriers are found to decrease with increasing F~-substitution, which is in line with experimental rate constants k_(ex). The log k_(ex) of AIF_3H_2O)~(3) and AIF_4(H_20)_(2-) are predicted by three ways. The results indicate that the correlation between log k,x and Al—0 bond length as well as the given transmission coefficient allows experimental rate constants to be predicted, whereas the correlation between log k_(ex) and activation free energy is poor; (3) the environmental significance of this work is elucidated by the extension toward three fields, that is, polyaluminum system, monomer Al-organic system and other metal ions system with high charge-to-radius ratio.

机译：进行了密度泛函理论（DFT）计算，研究了Al-F配合物的结构，〜（19）F和〜（27）Al NMR化学位移及其水交换反应。本文进行了以下研究：（1）在B3LYP / 6-311 + G **的水平下获得了典型的Al-F水性复合物的微观性质。 Al〜OH_2键长随F〜逐渐取代内球H_20而增加，说明F〜配体的致阴效果。 AI-0H_2与氟化物的反式距离比其他Al-0H_2的距离长，这说明了F〜配体的反式作用。使用GIAO方法在HF / 6-311 + G **水平上分别相对于RH_20）_6-和AI（H_20）6〜（3+）参考值计算19F和〜（27）AI NMR化学位移。与可用的实验值一致； {2）通过模拟[AI（H_20）6-iFi] l3'1 +（/ = 1-4）的水交换反应，观察到解离（D）活化机制。发现活化能垒随着F〜取代的增加而降低，这与实验速率常数k_（ex）一致。通过三种方式预测AIF_3H_2O）〜（3）和AIF_4（H_20）_（2-）的log k_（ex）。结果表明，log k，x和Al-0键长之间的相关性以及给定的传输系数可以预测实验速率常数，而log k_（ex）与活化自由能之间的相关性较弱；（3）通过向三个领域扩展，即多铝体系，单体铝-有机体系和其他具有高电荷-半径比的金属离子体系，阐明了这项工作的环境意义。

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来源
《Environmental Science & Technology》 |2011年第1期|p.288-293|共6页
作者
XIAOYAN JIN; ZHAOSHENG QIAN; BANGMEI LU; WENJING YANG; SHUPING BI;
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作者单位

School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry of China & Key Laboratory of MOEfor Life Science, Nanjing University, Nanjing 210093, China;

School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry of China & Key Laboratory of MOEfor Life Science, Nanjing University, Nanjing 210093, China,College of Chemistry and Life Science, Zhejiang Normal University, Jinhua, Zhejiang 321004, China;

School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry of China & Key Laboratory of MOEfor Life Science, Nanjing University, Nanjing 210093, China;

School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry of China & Key Laboratory of MOEfor Life Science, Nanjing University, Nanjing 210093, China;

School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry of China & Key Laboratory of MOEfor Life Science, Nanjing University, Nanjing 210093, China;

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收录信息美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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Density Functional Theory Study on Aqueous Aluminum-Fluoride Complexes: Exploration of the Intrinsic Relationship between Water-Exchange Rate Constants and Structural Parameters for Monomer Aluminum Complexes

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