Revealing the Structure of Transition Metal Complexes of Formaldoxime | Sciact

Revealing the Structure of Transition Metal Complexes of Formaldoxime Научная публикация

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, Leninsky prospect, 47, Moscow, Russia, 119991
2	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28, Moscow, Russia, 119991
3	Shubnikov Institute of Crystallography of FSRC “Crystallography and Photonics,” Russian Academy of Sciences, Leninsky prospect, 59, Moscow, Russia, 119991
4	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, 5 Ac. Lavrentiev Avenue, Novosibirsk, Russia, 630090
5	Plekhanov Russian University of Economics, Stremyanny per. 36, Moscow, Russia, 117997

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.

Golovanov I.S. , Malykhin R.S. , Lesnikov V.K. , Nelyubina Y.V. , Novikov V.V. , Frolov K.V. , Stadnichenko A.I. , Tretyakov E.V. , Ioffe S.L. , Sukhorukov A.Y.
Revealing the Structure of Transition Metal Complexes of Formaldoxime
Inorganic Chemistry. 2021. V.60. N8. P.5523-5537. DOI: 10.1021/acs.inorgchem.0c03362 WOS Scopus OpenAlex

Web of science:	WOS:000642344900015
Scopus:	2-s2.0-85105104362
OpenAlex:	W3142585236

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