[M(NH)] [M(CO)]（M，M = Co，Rh）和 K[Rh(NH)] [Rh(CO)]∙6HO 的双配合物盐的晶体结构和热性质。

Crystal Structure and Thermal Properties of Double-Complex Salts [M(NH)][M(CO)] (M, M = Co, Rh) and K[Rh(NH)][Rh(CO)]∙6HO.

机构信息

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia.

Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia.

出版信息

Int J Mol Sci. 2023 Jul 31;24(15):12279. doi: 10.3390/ijms241512279.

DOI:10.3390/ijms241512279

PMID:37569655

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10418981/

Abstract

Here, seven new double-complex salts, [M(NH)][M(CO)] (M, M = Co, Rh) and K[Rh(NH)][Rh(CO)]∙6HO types, are synthesised. The crystal structure and composition of DCS (double-complex salts) are studied by SCXRD, XRD, CHN and IR methods. The complex salts of the [M(NH)][M(CO)] (M, M = Co, Rh) type can be crystallised both as a crystalline hydrate [M(NH)][M(CO)]·3HO (sp. gr. -3) and as an anhydrous complex (sp. gr. -1) depending on the synthesis conditions. The process of [Rh(NH)][Rh(CO)] formation is significantly dependent on the synthesis temperature. At room temperature, a mixture is formed comprising [Rh(NH)][Rh(CO)] and K[Rh(NH)][Rh(CO)]∙6HO, while the [Rh(NH)][Rh(CO)] target product crystallises at elevated temperatures. The thermal behaviour of double-complex salts is studied by the STA, EGA-MS, IR and XRD methods. The complete decomposition of complex salts in helium and hydrogen atmospheres resulting in metals or CoRh solid solutions is achieved at temperatures of 320-450 °C.

摘要

在这里，合成了七种新型双核配合物盐[M(NH)][M(CO)]（M，M = Co，Rh）和 K[Rh(NH)][Rh(CO)]·6H2O 型。通过 SCXRD、XRD、CHN 和 IR 方法研究了 DCS（双核配合物盐）的晶体结构和组成。[M(NH)][M(CO)]（M，M = Co，Rh）型的配合物盐可以根据合成条件结晶为含水晶体[M(NH)][M(CO)]·3H2O（-3 密度）和无水配合物（-1 密度）。[Rh(NH)][Rh(CO)]的形成过程明显取决于合成温度。在室温下，形成了包含[Rh(NH)][Rh(CO)]和 K[Rh(NH)][Rh(CO)]·6H2O 的混合物，而目标产物[Rh(NH)][Rh(CO)]则在高温下结晶。通过 STA、EGA-MS、IR 和 XRD 方法研究了双核配合物盐的热行为。在 320-450°C 的温度下，在氦气和氢气气氛中，通过完全分解复杂盐可以得到金属或 CoRh 固溶体。