Crystal Structure, Electronic Structure, and Solid‐State Electrochemistry of Cluster Complexes of M3Se74+ (M = Mo, W) with Noninnocent o‐Phenanthroline and Se22– Ligands
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
European Journal of Inorganic Chemistry
ISSN: 1434-1948
, E-ISSN: 1099-0682
|
| Вых. Данные |
Год: 2008,
Номер: 25,
Страницы: 3964-3969
Страниц
: 6
DOI:
10.1002/ejic.200800070
|
| Ключевые слова |
Cyclic voltammetry, Electronic structure, Molybdenum, Tungsten chalcogens |
| Авторы |
Gushchin Artyom L.
1,2
,
Sokolov Maxim N.
1,2
,
Peresypkina Eugenia V.
1
,
Virovets Alexandr V.
1
,
Kozlova Svetlana G.
1,2,3
,
Zakharchuk Nina F.
1
,
Fedin Vladimir P.
1,2
|
| Организации |
| 1 |
Nikolayev Institute of Inorganic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Prospekt Lavrentyeva, 3, Russian Federation
|
| 2 |
Novosibirsk State University, 630090 Novosibirsk, ulitsa Pirogova, 2, Russian Federation
|
| 3 |
Boreskov Institute of Catalysis, Russian Academy of Sciences, 630090 Novosibirsk, Prospekt Lavrentyeva, 5, Russian
|
|
Информация о финансировании (4)
|
1
|
Российский фонд фундаментальных исследований
|
05-03-32126
|
|
2
|
Президиум РАН
|
|
|
3
|
Региональный общественный Фонд содействия отечественной науке
|
|
|
4
|
Совет по грантам Президента Российской Федерации
|
МД-7072.2006.3
|
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.