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含四烷基铵阳离子的四硝酸钯(II)盐:结构方面、反应活性及在催化应用中钯沉积的适用性

Tetranitratopalladate(II) Salts with Tetraalkylammonium Cations: Structural Aspects, Reactivity, and Applicability toward Palladium Deposition for Catalytic Applications.

作者信息

Vasilchenko Danila, Topchiyan Polina, Berdyugin Semen, Plyusnin Pavel, Shayapov Vladimir, Baidina Iraida, Komarov Vladislav, Bukhtiyarov Andrey, Gerasimov Evgeny

机构信息

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Science, 630090 Novosibirsk, Russian Federation.

Boreskov Institute of Catalysis, 630090 Novosibirsk, Russia.

出版信息

Inorg Chem. 2021 Mar 1;60(5):2983-2995. doi: 10.1021/acs.inorgchem.0c03038. Epub 2021 Feb 10.

DOI:10.1021/acs.inorgchem.0c03038
PMID:33565855
Abstract

A series of salts (RN)[Pd(NO)] (R = CH, CH, n-CH; -) were synthesized in high yield from a nitric acid solution of palladium. The salts were characterized by a combination of physicochemical methods, and their crystal structures were determined by X-ray diffraction. The conformation of the [Pd(NO)] anion was studied in detail using crystal structure data and density functional theory calculations. A combination of nonhygroscopicity and stability under normal conditions, together with thermolability, high solubility in various solvents, and the lability of nitrato ligands, makes salts - valuable starting materials for the synthesis of Pd compounds and the preparation of Pd-containing catalysts. In this work, these applications were illustrated by the synthesis of heteroleptic Pd(II) nitrato complexes with N-donor ligands and the preparation of PdNi/SiO catalysts, which worked well in H generation from hydrazine hydrate. Generally, it was shown that up to several weight percent of Pd can be deposited on various oxide/hydroxide supports using a straightforward chemisorption procedure from acetone solutions of -.

摘要

一系列盐(RN)[Pd(NO)](R = CH、CH、n-CH;-)由钯的硝酸溶液高产率合成。这些盐通过多种物理化学方法进行表征,其晶体结构通过X射线衍射确定。利用晶体结构数据和密度泛函理论计算详细研究了[Pd(NO)]阴离子的构象。非吸湿性和正常条件下的稳定性,以及热稳定性、在各种溶剂中的高溶解性和硝酸根配体的不稳定性,使得这些盐成为合成钯化合物和制备含钯催化剂的有价值的起始原料。在这项工作中,通过合成含氮供体配体的杂配钯(II)硝酸根配合物以及制备PdNi/SiO催化剂来说明这些应用,该催化剂在水合肼制氢中表现良好。一般来说,结果表明,使用来自-丙酮溶液的直接化学吸附程序,高达百分之几重量的钯可以沉积在各种氧化物/氢氧化物载体上。

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