The Synthesis, Characterization, and Structure of (ThioH) 2 [OsX 6 ] (X = Cl, Br)
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Polyhedron
ISSN: 0277-5387
|
| Вых. Данные |
Год: 2017,
Том: 134,
Страницы: 114-119
Страниц
: 6
DOI:
10.1016/j.poly.2017.05.057
|
| Ключевые слова |
Osmium halido complexes; Thiourea; Protonation; IR and UV–Vis spectroscopy;
Synchrotron X-ray diffraction |
| Авторы |
Rudnitskaya Olga V.
1
,
Kultyshkina Ekaterina K.
1
,
Dobrokhotova Ekaterina V.
1
,
Podvoyskaya Viktoriya S.
1
,
Dorovatovskii Pavel V.
2
,
Lazarenko Vladimir A.
2
,
Zubavichus Yan V.
2
,
Khrustalev Victor N.
1
|
| Организации |
| 1 |
Department of Inorganic Chemistry, Peoples’ Friendship University of Russia (RUDN University)
|
| 2 |
National Research Center ‘‘Kurchatov Institute”
|
|
Novel osmium complexes (ThioH)2[OsCl6] (1) and (ThioH)2[OsBr6] (2) have been synthesized via the interaction of H2[OsX6] (X = Cl, Br) with thiourea (Thio) in concentrated HX and characterized by chemical analysis, potentiometry, IR- and UV–Vis spectroscopy, X-ray powder and single-crystal diffraction. UV–Vis spectroscopy of 1 and 2 in solutions supports the preservation of [OsX6]2− ions that however demonstrate considerable solvatochromism. The longer-wavelength bands experience a hypsochromic shift with respect to the crystalline state. Intense bands of Os-halogen vibrations in ATR IR spectra are red-shifted with respect to those for K2[OsX6]. The complexes are isostructural and crystallized in the triclinic space group , Z = 1. Unit cell parameters are for 1: a = 7.1800(14) Å, b = 7.2700(15) Å, c = 7.7800(16) Å, α = 78.89(3)°, β = 87.83(3)°, γ = 65.11(3)°; for 2: a = 7.3169(15) Å, b = 7.5504(15) Å, c = 8.2065(16) Å, α = 80.00(3)°, β = 88.55(3)°, γ = 63.37(3)°. The cations (NH2)2CSH+ and anions [OsX6]2− are assembled into two-tier layers by N–H…X and S–H…X hydrogen-bonds and S…X non-valent contacts.