Mixed-metal clusters with a {Re3Mo3Se8} core: from a polymeric solid to soluble species with multiple redox transitions. Issue 10 (9th February 2018)

• Record Type: Journal Article
• Authors: Muravieva, Viktoria K.; Gayfulin, Yakov M.; Ryzhikov, Maxim R.; Novozhilov, Igor N.; Samsonenko, Denis G.; Piryazev, Dmitry A.; Yanshole, Vadim V.; Naumov, Nikolay G.
• Is Part Of: Dalton transactions. Volume 47:Issue 10(2018)
• Page Start: 3366
• Page End: 3377
• Publication Date: 2018-02-09
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt03571c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Soluble compounds based on new heterometallic {Re3 Mo3 Se8 } n cluster cores were synthesized and investigated. Abstract : Cluster compounds based on a new {Re3 Mo3 Se8 } n core were obtained and studied. The polymeric solid K6 [Re3 Mo3 Se8 (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 [Re3 Mo3 Se8 (CN)6 ]·11H2 O (2 ) and Cs5 [Re3 Mo3 Se8 (CN)6 ]·H2 O (3 ) were prepared from compound1 . Crystal structures of the diamagnetic compounds2 and3 contain a cluster anion [Re3 Mo3 Se8 (CN)6 ] 5− with a 22-electronic core {Re3 Mo3 Se8 } + . Metathesis reaction followed by recrystallization from CH3 CN yielded paramagnetic salt (Ph4 P)4 [Re3 Mo3 Se8 (CN)6 ]·2CH3 CN (4 ) containing the {Re3 Mo3 Se8 } 2+ core with 21 CVE. Cyclic voltammetry of the solution of4 displayed three quasi-reversible waves with E 1/2 = −0.325, −0.818 and −1.410 V vs . Ag/AgCl electrode indicating the presence of [Re3 Mo3 Se8 (CN)6 ] 4−/5−/6−/7− transitions. Electronic structure calculations showed that both mer - and fac -isomers of [Re3 Mo3 Se8 (CN)6 ] n − clusters undergo great distortion when the number of CVE decreases.