Revealing the Structure of Transition Metal Complexes of Formaldoxime Full article
Journal |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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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 |
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Affiliations |
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Funding (1)
1 | Russian Foundation for Basic Research | 20-33-70188 (АААА-А19-119120490140-4) |
Abstract:
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.
Cite:
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
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
Dates:
Submitted: | Nov 12, 2020 |
Published online: | Apr 7, 2021 |
Published print: | Apr 19, 2021 |
Identifiers:
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 |