Revealing the Structure of Transition Metal Complexes of Formaldoxime
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Inorganic Chemistry
ISSN: 0020-1669
, E-ISSN: 1520-510X
|
| Вых. Данные |
Год: 2021,
Том: 60,
Номер: 8,
Страницы: 5523-5537
Страниц
: 15
DOI:
10.1021/acs.inorgchem.0c03362
|
| Авторы |
Golovanov Ivan S.
1
,
Malykhin Roman S.
1
,
Lesnikov Vladislav K.
1
,
Nelyubina Yulia V.
2
,
Novikov Valentin V.
2
,
Frolov Kirill V.
3
,
Stadnichenko Andrey I.
4
,
Tretyakov Evgeny V.
1
,
Ioffe Sema L.
1
,
Sukhorukov Alexey Yu.
1,5
|
| Организации |
| 1 |
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia 119991
|
| 2 |
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia 119991
|
| 3 |
Shubnikov Institute of Crystallography of FSRC “Crystallography and Photonics,” Russian Academy of Sciences, Moscow, Russia 119991
|
| 4 |
Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia 630090
|
| 5 |
Plekhanov Russian University of Economics, Moscow, Russia 117997
|
|
Информация о финансировании (1)
|
1
|
Российский фонд фундаментальных исследований
|
20-33-70188 (АААА-А19-119120490140-4)
|
Aerobic reactions of iron(III), nickel(II), and manganese(II) chlorides with formaldoxime cyclotrimer (tfoH3) and 1,4,7-triazacyclononane (tacn) produce indefinitely stable complexes of general formula [M(tacn)(tfo)]Cl. Although the formation of formaldoxime complexes has been known since the end of 19th century and applied in spectrophotometric determination of d-metals (formaldoxime method), the structure of these coordination compounds remained elusive until now. According to the X-ray analysis, [M(tacn)(tfo)]+ cation has a distorted adamantane-like structure with the metal ion being coordinated by three oxygen atoms of deprotonated tfoH3 ligand. The metal has a formal +4 oxidation state, which is atypical for organic complexes of iron and nickel. Electronic structure of [M(tacn)(tfo)]+ cations was studied by XPS, NMR, cyclic (CV) and differential pulse (DPV) voltammetries, Mössbauer spectroscopy, and DFT calculations. Unusual stabilization of high-valent metal ion by tfo3– ligand was explained by the donation of electron density from the nitrogen atom to the antibonding orbital of the metal–oxygen bond via hyperconjugation as confirmed by the NBO analysis. All complexes [M(tacn)(tfo)]Cl exhibited high catalytic activity in the aerobic dehydrogenative dimerization of p-thiocresol under ambient conditions.