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

V.K. Muravieva (1) , Y.M. Gayfulin , M.R. Ryzhikov (2) , I.N. Novozhilov , D.G. Samsonenko (2) , D.A. Piryazev (2) , V.V. Yanshole (2) , N.G. Naumov (2)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 NSU - Novosibirsk State University

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

Domains: Chemical Sciences

V.K. Muravieva, Y.M. Gayfulin, M.R. Ryzhikov, I.N. Novozhilov, D.G. Samsonenko, et al.. Mixed-metal clusters with a {Re3Mo3Se8} core From a polymeric solid to soluble species with multiple redox transitions. Dalton Transactions, 2018, 47 (10), pp.3366-3377. ⟨10.1039/c7dt03571c⟩. ⟨hal-01740141⟩