Hypervalent Bonding in Alkali-Metal Cyanides Detected by High-Temperature Mass Spectrometry (高温質量分析特集号)
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概要
- 論文の詳細を見る
We present a combined experimental and theoretical study on the nature of hypervalent bonding in such molecules as Li2CN, Na2CN, K2CN, and Li2OH. The molecules M2CN (M=Li, Na, K) were observed in the vapor over a mixture of alkali metals and sodium cyanide by high-temperature Knudsen effusion mass spectrometry and Li2OH was detected by time-of-flight mass spectrometry for a molecular beam generated by laser ablation of slightly oxidized lithium metal. Despite their unusual stoichiometries, these molecules were confirmed to be thermodynamically more stable than the corresponding octet molecules (MCN, LiOH). Computational geometry optimization gives four possible structural isomers to each M2CN molecule; i.e., two planar structures with Cs symmetry and two linear structures with C∞v symmetry. The planar M2CN molecules are favored and best described as a complex of the CN- anion with the M2+ cation. The extra valence electron in SOMO contributes to M-M bonding to form the M2+ unit. The linear M2CN molecules are “electronomers” described as M+(CN)-M· and M·(CN)-M+. The Li2OH molecule with C2v symmetry comprises the Li2+ and OH- units, and the electrostatic attraction affords the stable molecule, similar to the planar M2CN.
- 日本質量分析学会の論文
- 1999-02-01
著者
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横山 啓一
日本原子力研究開発機構
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Tanaka Hiromasa
Department Of Agro-bioscience Faculty Of Agriculture Iwate University
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Yokoyama Keiichi
Department Of Biotechnology Graduate School Of Agricultre And Life Science The University Of Tokyo
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Yokoyama Keiichi
Department Of Materials Science Japan Atomic Energy Research Institute
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Hashimoto Masashi
Department Of Chemistry Faculty Of Science Kobe University
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Hashimoto Masashi
Department Of Materials Science Japan Atomic Energy Research Institute
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Kudo Hiroshi
Department Of Biology Faculty Of Science Kobe University
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Tanaka Hiromasa
Department Of Chemistry Graduate School Of Science Tohoku University
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Yokoyama Keiichi
Quantum Beam Science Directorate, Kansai Photon Science Institute, Japan Atomic Energy Agency, 8-1 Umemidai, Kizu, Kyoto 619-0215, Japan
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