Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+ (M = Mo, W) with Noninnocent o‐Phenanthroline and Se22– Ligands Full article
Journal |
European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682 |
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Output data | Year: 2008, Number: 25, Pages: 3964-3969 Pages count : 6 DOI: 10.1002/ejic.200800070 | ||||||
Tags | Cyclic voltammetry, Electronic structure, Molybdenum, Tungsten chalcogens | ||||||
Authors |
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Affiliations |
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Funding (4)
1 | Russian Foundation for Basic Research | 05-03-32126 |
2 | Президиум РАН | |
3 | Russian Science Support Foundation | |
4 | Council for Grants of the President of the Russian Federation | МД-7072.2006.3 |
Abstract:
The crystal, molecular, and electronic structure as well as the electrochemical behavior of o-phenanthroline complexes [M3Se7(o-phen)3]X4 (M = Mo, W; X = Cl, Br) were investigated. Recrystallization of [Mo3Se7(o-phen)3]Br4 from concentrated hydrochloric acid gave crystals corresponding to [Mo3(µ3-Se)(µ2-Se2)3(o-phen)3]Cl4·12H2O, for which X-ray analysis was performed. The bromide is isostructural. Solid-state cyclic voltammetry shows that [M3Se7(o-phen)3]Br4 (M= Mo, W) undergoes reversible three-electron reduction, which is phen-centered with strong delocalization on the metal. DFT calculations for {[Mo3Se7(o-phen)3]Br}3+, [Mo3-Se7(o-phen)3]4+, and
{[Mo3Se7(o-phen)3]Br}0 support the correct formulation of the reduction process. Strong interactions between the Cl– or Br– and Se2 ligands of the M3Se7 cluster, observed in the crystal, can be described as donor–acceptor covalent bonding and are important enough to influence the redox behavior of the cluster.
Cite:
Gushchin A.L.
, Sokolov M.N.
, Peresypkina E.V.
, Virovets A.V.
, Kozlova S.G.
, Zakharchuk N.F.
, Fedin V.P.
Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+ (M = Mo, W) with Noninnocent o‐Phenanthroline and Se22– Ligands
European Journal of Inorganic Chemistry. 2008. N25. P.3964-3969. DOI: 10.1002/ejic.200800070 WOS Scopus РИНЦ
Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+ (M = Mo, W) with Noninnocent o‐Phenanthroline and Se22– Ligands
European Journal of Inorganic Chemistry. 2008. N25. P.3964-3969. DOI: 10.1002/ejic.200800070 WOS Scopus РИНЦ
Dates:
Submitted: | Jan 22, 2008 |
Published online: | Jul 25, 2008 |
Published print: | Sep 1, 2008 |
Identifiers:
Web of science | WOS:000259252200009 |
Scopus | 2-s2.0-53549094958 |
Elibrary | 13597117 |
Chemical Abstracts | 2008:1149864 |
Chemical Abstracts (print) | 151:540693 |
OpenAlex | W2016533186 |