Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M 3 Se 7  4+  (M = Mo, W) with Noninnocent  o ‐Phenanthroline and Se 2  2–  Ligands | Zendy

Gushchin Artyom L. | Zendy; Sokolov Maxim N. | Zendy; Peresypkina Eugenia V. | Zendy; Virovets Alexandr V. | Zendy; Kozlova Svetlana G. | Zendy; Zakharchuk Nina F. | Zendy; Fedin Vladimir P. | Zendy

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Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M 3 Se 7 4+ (M = Mo, W) with Noninnocent o ‐Phenanthroline and Se 2 2– Ligands

Author(s) -

Gushchin Artyom L.,

Sokolov Maxim N.,

Peresypkina Eugenia V.,

Virovets Alexandr V.,

Kozlova Svetlana G.,

Zakharchuk Nina F.,

Fedin Vladimir P.

Publication year - 2008

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.200800070

Subject(s) - chemistry , isostructural , crystallography , electrochemistry , crystal structure , redox , phenanthroline , cluster (spacecraft) , bromide , delocalized electron , covalent bond , inorganic chemistry , electrode , organic chemistry , computer science , programming language

The crystal, molecular, and electronic structure as well as the electrochemical behavior of o ‐phenanthroline complexes [M 3 Se 7 ( o ‐phen) 3 ]X 4 (M = Mo, W; X = Cl, Br) were investigated. Recrystallization of [Mo 3 Se 7 ( o ‐phen) 3 ]Br 4 from concentrated hydrochloric acid gave crystals corresponding to [Mo 3 (μ 3 ‐Se)(μ 2 ‐Se 2 ) 3 ( o ‐phen) 3 ]Cl 4 · 12H 2 O, for which X‐ray analysis was performed. The bromide is isostructural. Solid‐state cyclic voltammetry shows that [M 3 Se 7 ( o ‐phen) 3 ]Br 4 (M = Mo, W) undergoes reversible three‐electron reduction, which is phen‐centered with strong delocalization on the metal. DFT calculations for {[Mo 3 Se 7 ( o ‐phen) 3 ]Br} 3+ , [Mo 3 Se 7 ( o ‐phen) 3 ] 4+ , and {[Mo 3 Se 7 ( o ‐phen) 3 ]Br} 0 support the correct formulation of the reduction process. Strong interactions between the Cl – or Br – and Se 2 ligands of the M 3 Se 7 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.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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