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Symmetry of three-center, four-electron bonds
Chemical Science ( IF 7.6 ) Pub Date : 2020-06-30 , DOI: 10.1039/d0sc02076a Ann Christin Reiersølmoen 1, 2, 3, 4 , Stefano Battaglia 5, 6, 7, 8 , Sigurd Øien-Ødegaard 4, 9, 10, 11 , Arvind Kumar Gupta 6, 7, 8, 12 , Anne Fiksdahl 1, 2, 3, 4 , Roland Lindh 5, 6, 7, 8 , Máté Erdélyi 5, 6, 7, 8
Chemical Science ( IF 7.6 ) Pub Date : 2020-06-30 , DOI: 10.1039/d0sc02076a Ann Christin Reiersølmoen 1, 2, 3, 4 , Stefano Battaglia 5, 6, 7, 8 , Sigurd Øien-Ødegaard 4, 9, 10, 11 , Arvind Kumar Gupta 6, 7, 8, 12 , Anne Fiksdahl 1, 2, 3, 4 , Roland Lindh 5, 6, 7, 8 , Máté Erdélyi 5, 6, 7, 8
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Three-center, four-electron bonds provide unusually strong interactions; however, their nature remains ununderstood. Investigations of the strength, symmetry and the covalent versus electrostatic character of three-center hydrogen bonds have vastly contributed to the understanding of chemical bonding, whereas the assessments of the analogous three-center halogen, chalcogen, tetrel and metallic ![[small sigma, Greek, circumflex]](https://www.rsc.org/images/entities/char_e111.gif)
-type long bonding are still lagging behind. Herein, we disclose the X-ray crystallographic, NMR spectroscopic and computational investigation of three-center, four-electron [D–X–D]+ bonding for a variety of cations (X+ = H+, Li+, Na+, F+, Cl+, Br+, I+, Ag+ and Au+) using a benchmark bidentate model system. Formation of a three-center bond, [D–X–D]+ is accompanied by an at least 30% shortening of the D–X bonds. We introduce a numerical index that correlates symmetry to the ionic size and the electron affinity of the central cation, X+. Providing an improved understanding of the fundamental factors determining bond symmetry on a comprehensive level is expected to facilitate future developments and applications of secondary bonding and hypervalent chemistry.
中文翻译：
三中心四电子键的对称性
三中心，四电子键提供了异常强的相互作用。但是，它们的性质仍然未被理解。对三中心氢键的强度，对称性以及共价键与静电特性的研究极大地促进了对化学键的理解，而对类似的三中心卤素，硫属元素，蝶形和金属型长键的评估仍在进行中落后。在此，我们公开了各种阳离子（X + = H +，Li +，Na +，三价，三价，四电子[D–X–D] +键）的X射线晶体学，NMR光谱和计算研究F +，氯+，Br +，I +，Ag +和Au +）使用基准双齿模型系统。三中心键[D–X–D] +的形成至少会缩短D–X键30％。我们引入了一个数值索引，该索引使对称性与中心阳离子X +的离子大小和电子亲和力相关。全面了解确定键对称性的基本因素，有望促进次级键和高价化学的未来发展和应用。
更新日期：2020-08-05
-type long bonding are still lagging behind. Herein, we disclose the X-ray crystallographic, NMR spectroscopic and computational investigation of three-center, four-electron [D–X–D]+ bonding for a variety of cations (X+ = H+, Li+, Na+, F+, Cl+, Br+, I+, Ag+ and Au+) using a benchmark bidentate model system. Formation of a three-center bond, [D–X–D]+ is accompanied by an at least 30% shortening of the D–X bonds. We introduce a numerical index that correlates symmetry to the ionic size and the electron affinity of the central cation, X+. Providing an improved understanding of the fundamental factors determining bond symmetry on a comprehensive level is expected to facilitate future developments and applications of secondary bonding and hypervalent chemistry.
中文翻译：
三中心四电子键的对称性
三中心，四电子键提供了异常强的相互作用。但是，它们的性质仍然未被理解。对三中心氢键的强度，对称性以及共价键与静电特性的研究极大地促进了对化学键的理解，而对类似的三中心卤素，硫属元素，蝶形和金属
型长键的评估仍在进行中落后。在此，我们公开了各种阳离子（X + = H +，Li +，Na +，三价，三价，四电子[D–X–D] +键）的X射线晶体学，NMR光谱和计算研究F +，氯+，Br +，I +，Ag +和Au +）使用基准双齿模型系统。三中心键[D–X–D] +的形成至少会缩短D–X键30％。我们引入了一个数值索引，该索引使对称性与中心阳离子X +的离子大小和电子亲和力相关。全面了解确定键对称性的基本因素，有望促进次级键和高价化学的未来发展和应用。
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