Kinetics Aspects of the Reversible Assembly of Copper in Heterometallic Mo3CuS4Clusters with 4,4'-Di-tert-butyl-2,2'-bipyridine.
Treatment of the triangular [Mo3S4Cl3(dbbpy)3]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal cluster [Mo3(CuCl)S4Cl3(dbbpy)3][CuCl2] ([2][CuCl2]), 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 M3M'S4cluster. 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 CuCl2-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 M3S4clusters and their heterometallic M3M'S4derivatives 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.
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.
Jose Ángel
JÁ
Pino-Chamorro
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , 630090 Novosibirsk, Russia.
Yuliya A
YA
Laricheva
Dept. de Química Física i Analítica, Universitat Jaume I , Av. Sos Baynat s/n, 12071 Castelló, Spain.
Eva
E
Guillamón
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.
M Jesús
MJ
Fernández-Trujillo
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.
Andrés G
AG
Algarra
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , 630090 Novosibirsk, Russia.|Dept. de Química Física i Analítica, Universitat Jaume I , Av. Sos Baynat s/n, 12071 Castelló, Spain.|Novosibirsk State University , 630090 Novosibirsk, Russia.
Artem L
AL
Gushchin
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , 630090 Novosibirsk, Russia.|Dept. de Química Física i Analítica, Universitat Jaume I , Av. Sos Baynat s/n, 12071 Castelló, Spain.|Novosibirsk State University , 630090 Novosibirsk, Russia.
Pavel A
PA
Abramov
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.
Emilio
E
Bustelo
Dept. de Química Física i Analítica, Universitat Jaume I , Av. Sos Baynat s/n, 12071 Castelló, Spain.
Rosa
R
Llusar
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , 630090 Novosibirsk, Russia.|Novosibirsk State University , 630090 Novosibirsk, Russia.
Maxim N
MN
Sokolov
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.
Manuel G
MG
Basallote