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.

Язык оригиналаанглийский
Страницы (с-по)3366-3377
Число страниц12
ЖурналDalton Transactions
Номер выпуска10
СостояниеОпубликовано - 14 мар 2018

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