Revealing the Structure of Transition Metal Complexes of Formaldoxime | Sciact - CRIS-system of Boreskov Institute of Catalysis

Revealing the Structure of Transition Metal Complexes of Formaldoxime Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2021, Volume: 60, Number: 8, Pages: 5523-5537 Pages count : 15 DOI: 10.1021/acs.inorgchem.0c03362

Tags

Catalyst activity; Chlorine compounds; Electronic structure; Energy dispersive X ray analysis; Iron compounds; Ligands; Metal complexes; Metal ions; Nickel compounds; Oxygen; Positive ions; Transition metals; X ray diffraction analysis

Authors

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

Affiliations

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

Funding (1)

Russian Foundation for Basic Research

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.

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 РИНЦ ANCAN PMID OpenAlex

Submitted:	Nov 12, 2020
Published online:	Apr 7, 2021
Published print:	Apr 19, 2021

Web of science:	WOS:000642344900015
Scopus:	2-s2.0-85105104362
Elibrary:	46043648
Chemical Abstracts:	2021:807640
Chemical Abstracts (print):	174:772492
PMID:	33826845
OpenAlex:	W3142585236

DB	Citing
Scopus	6
Web of science	5
Elibrary	6
OpenAlex	6