Pino-Chamorro Jose Ángel, Laricheva Yuliya A, Guillamón Eva, Fernández-Trujillo M Jesús, Algarra Andrés G, Gushchin Artem L, Abramov Pavel A, Bustelo Emilio, Llusar Rosa, Sokolov Maxim N, Basallote Manuel G
Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, and Instituto de Biomoléculas, INBIO, Universidad de Cádiz , Avda. República Saharahui s/n, Puerto Real, 11510 Cádiz, Spain.
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , 630090 Novosibirsk, Russia.
Inorg Chem. 2016 Oct 3;55(19):9912-9922. doi: 10.1021/acs.inorgchem.6b01878. Epub 2016 Sep 22.
Treatment of the triangular [MoSCl(dbbpy)]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal cluster [Mo(CuCl)SCl(dbbpy)][CuCl] ([2][CuCl]), whose crystal structure was determined by X-ray diffraction (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). This species, which contains two distinct types of Cu(I), is the first example of a diimine-functionalized heterometallic MM'S cluster. Kinetics studies on both the formation of the cubane from the parent trinuclear cluster and its dissociation after treatment with halides, supported by NMR, electrospray ionization mass spectrometry, cyclic voltammetry, and density functional theory calculations, are provided. On the one hand, the results indicate that addition of Cu(I) to [1] is so fast that its kinetics can be monitored only by cryo-stopped flow at -85 °C. On the other hand, the release of the CuCl unit in [2] is also a fast process, which is unexpectedly assisted by the CuCl counteranion in a process triggered by halide (X) anions. The whole set of results provide a detailed picture of the assembly-disassembly processes in this kind of cluster. Interconversion between trinuclear MS clusters and their heterometallic MM'S derivatives can be a fast process occurring readily under the conditions employed during reactivity and catalytic studies, so their occurrence is a possibility that must be taken into account in future studies.
