Cyanides, Isocyanides, and Hydrides of Zn, Cd and Hg from Metal Atom and HCN Reactions: Matrix Infrared Spectra and Electronic Structure Calculations,ChemPhysChem

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Cyanides, Isocyanides, and Hydrides of Zn, Cd and Hg from Metal Atom and HCN Reactions: Matrix Infrared Spectra and Electronic Structure Calculations
ChemPhysChem ( IF 2.3 ) Pub Date : 2021-08-13 , DOI: 10.1002/cphc.202100011
Hongmin Li ₁ , Yetsedaw A Tsegaw ₁ , Lester Andrews ₂ , Carl Trindle ₂ , Han-Gook Cho ₃ , Tony Stüker ₁ , Helmut Beckers ₁ , Sebastian Riedel ₁

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Zinc and cadmium atoms from laser ablation of the metals and mercury atoms ablated from a dental amalgam target react with HCN in excess argon during deposition at 5 K to form the MCN and MNC molecules and CN radicals. UV irradiation decreases the higher energy ZnNC isomer in favor of the lower energy ZnCN product. Cadmium and mercury atoms produce analogous MCN primary molecules. Laser ablation of metals also produces plume radiation which initiates H-atom detachment from HCN. The freed H atom can add to CN radical to produce the HNC isomer. The argon matrix also traps the higher energy but more intensely absorbing isocyanide molecules. Further reactions with H atoms generate HMCN and HMNC hydrides, which can be observed by virtue of their C−N stretches and intense M−H stretches. Computational modeling of IR spectra and relative energies guides the identification of reaction products by providing generally reliable frequency differences within the Zn, Cd and Hg family of products, and estimating isotopic shifts using to ¹³C and ¹⁵N isotopic substitution for comparison with experimental data.

中文翻译：

来自金属原子和 HCN 反应的 Zn、Cd 和 Hg 的氰化物、异氰化物和氢化物：基质红外光谱和电子结构计算

激光烧蚀金属的锌和镉原子以及从牙科汞合金靶上烧蚀的汞原子在 5 K 沉积期间与过量氩气中的 HCN 反应，形成 MCN 和 MNC 分子以及 CN 自由基。紫外线照射降低了较高能量的 ZnNC 异构体，有利于较低能量的 ZnCN 产物。镉和汞原子产生类似的 MCN 初级分子。金属的激光烧蚀也会产生羽状辐射，从而引发 H 原子从 HCN 脱离。游离的 H 原子可以与 CN 自由基加成生成 HNC 异构体。氩基体还捕获了更高能量但更强烈吸收的异氰化物分子。与 H 原子的进一步反应生成 HMCN 和 HMNC 氢化物，这可以通过它们的 CN 拉伸和强烈的 MH 拉伸观察到。¹³ C 和¹⁵ N 同位素置换用于与实验数据进行比较。

更新日期：2021-09-15

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