文章基本信息

标题：Eight-coordinate fluoride in a silicate double-four-ring
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作者：Maarten G. Goesten ; Roald Hoffmann ; F. Matthias Bickelhaupt 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2017
卷号：114
期号：5
页码：828-833
DOI：10.1073/pnas.1615742114
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Fluoride, nature’s smallest anion, is capable of covalently coordinating to eight silicon atoms. The setting is a simple and common motif in zeolite chemistry: the box-shaped silicate double-four-ring (D4R). Fluoride seeks its center. It is the strain of box deformation that keeps fluoride in the middle of the box, and freezes what would be a transition state in its absence. Hypervalent bonding ensues. Fluoride’s compactness works to its advantage in stabilizing the cage; chloride, bromide, and iodide do not bring about stabilization due to greater steric repulsion with the box frame. The combination of strain and hypervalent bonding, and the way they work in concert to yield this unusual case of multiple hypervalence, has potential for extension to a broader range of solid-state compounds.
关键词：chemical bonding ; main-group chemistry ; hypervalence ; zeolite chemistry