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Mixed-metal clusters with a {Re3Mo3Se8} core: from a polymeric solid to soluble species with multiple redox transitions

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Abstract

Cluster compounds based on a new {Re3Mo3Se8}n core were obtained and studied. The polymeric solid K6[Re3Mo3Se8(CN)4(CN)2/2] (1) containing 24 cluster valence electrons (CVE) was isolated as a result of high-temperature reaction. Water-soluble salts K5[Re3Mo3Se8(CN)6]·11H2O (2) and Cs5[Re3Mo3Se8(CN)6]·H2O (3) were prepared from compound 1. Crystal structures of the diamagnetic compounds 2 and 3 contain a cluster anion [Re3Mo3Se8(CN)6]5− with a 22-electronic core {Re3Mo3Se8}+. Metathesis reaction followed by recrystallization from CH3CN yielded paramagnetic salt (Ph4P)4[Re3Mo3Se8(CN)6]·2CH3CN (4) containing the {Re3Mo3Se8}2+ core with 21 CVE. Cyclic voltammetry of the solution of 4 displayed three quasi-reversible waves with E1/2 = −0.325, −0.818 and −1.410 V vs. Ag/AgCl electrode indicating the presence of [Re3Mo3Se8(CN)6]4−/5−/6−/7− transitions. Electronic structure calculations showed that both mer- and fac-isomers of [Re3Mo3Se8(CN)6]n clusters undergo great distortion when the number of CVE decreases.

Graphical abstract: Mixed-metal clusters with a {Re3Mo3Se8} core: from a polymeric solid to soluble species with multiple redox transitions

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Publication details

The article was received on 22 Sep 2017, accepted on 24 Jan 2018 and first published on 24 Jan 2018


Article type: Paper
DOI: 10.1039/C7DT03571C
Citation: Dalton Trans., 2018, Advance Article
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    Mixed-metal clusters with a {Re3Mo3Se8} core: from a polymeric solid to soluble species with multiple redox transitions

    V. K. Muravieva, Y. M. Gayfulin, M. R. Ryzhikov, I. N. Novozhilov, D. G. Samsonenko, D. A. Piryazev, V. V. Yanshole and N. G. Naumov, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C7DT03571C

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