End-On Cyanogen Complexes of Iridium, Palladium, and Platinum
文献类型：期刊论文
| 作者 | Chen, XT; Xiong, ZX; Andrews, L; Gong, Y |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2020 |
| 卷号 | 59期号:9页码:6489-6495 |
| 关键词 | MATRIX INFRARED-SPECTRA ANION PHOTOELECTRON-SPECTROSCOPY DENSITY-FUNCTIONAL CALCULATIONS LASER-ABLATED PLATINUM THEORETICAL INVESTIGATIONS COORDINATION CHEMISTRY HYDROGEN-CYANIDE BASIS-SETS ATOMS NICKEL |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/acs.inorgchem.0c00582 |
| 文献子类 | 期刊论文 |
| 英文摘要 | The cyanogen complexes of iridium, palladium, and platinum were prepared via the reactions of noble metal atoms with cyanogen in argon matrixes, and the product structures were determined by infrared spectroscopy and density functional theory calculations. These complexes were predicted to possess linear geometries with the metal center coordinated by the nitrogen atom of cyanogen in end-on fashions. On the basis of the B3LYP calculations, doublet, singlet, and singlet spin states are most stable for [Ir(NCCN)], [Pd(NCCN)], and [Pt(NCCN)]. Bonding analysis revealed the presence of electron donation from the polarized sigma - orbital of cyanogen into the empty metal d(z)(2) orbital and back-donation from the metal d(xz/yz) orbitals to the 2 pi(u) orbitals of cyanogen, the latter of which destabilizes the C-N bond and stabilizes the C-C bond. Such an effect causes an increase in C-N bond length by 0.01-0.015 angstrom and a decrease in C-C bond length by 0.013-0.02 angstrom for noble-metal-cyanogen complexes in comparison to the same bond in neutral cyanogen, and this is also consistent with the changes in vibrational frequencies. Although [Ir(NCCN)], [Pd(NCCN)], and [Pt(NCCN)] were formed spontaneously during sample annealing, neither cyanide nor isocyanide product was observed in the experiments, which is different from the cases of early transition, lanthanide, and actinide metals. |
| 语种 | 英语 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/32850]  |
| 专题 | 上海应用物理研究所_中科院上海应用物理研究所2011-2017年 |
| 作者单位 | 1.Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA 2.Chinese Acad Sci, Shanghai Inst Appl Phys, Dept Radiochem, Shanghai 201800, Peoples R China 3.Univ Chinese Acad Sci, Sch Nucl Sci & Technol, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Chen, XT,Xiong, ZX,Andrews, L,et al. End-On Cyanogen Complexes of Iridium, Palladium, and Platinum[J]. INORGANIC CHEMISTRY,2020,59(9):6489-6495. |
| APA | Chen, XT,Xiong, ZX,Andrews, L,&Gong, Y.(2020).End-On Cyanogen Complexes of Iridium, Palladium, and Platinum.INORGANIC CHEMISTRY,59(9),6489-6495. |
| MLA | Chen, XT,et al."End-On Cyanogen Complexes of Iridium, Palladium, and Platinum".INORGANIC CHEMISTRY 59.9(2020):6489-6495. |
入库方式： OAI收割
来源：上海应用物理研究所
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