Inorganic Chemistry, volume 60, issue 8, pages 5523-5537
Revealing the Structure of Transition Metal Complexes of Formaldoxime
Golovanov Ivan S
1
,
Malykhin Roman S
1
,
Lesnikov Vladislav K
1
,
Frolov Kirill V.
3
,
Tretyakov Evgeny
1
,
Ioffe Sema L.
1
,
Sukhorukov Alexey Yu
1, 5
3
Publication type: Journal Article
Publication date: 2021-04-07
Journal:
Inorganic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 4.6
ISSN: 00201669, 1520510X
Inorganic Chemistry
Physical and Theoretical Chemistry
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.
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3 publications, 60%
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Springer Nature
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1 publication, 20%
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- We do not take into account publications that without a DOI.
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Golovanov I. S. et al. Revealing the Structure of Transition Metal Complexes of Formaldoxime // Inorganic Chemistry. 2021. Vol. 60. No. 8. pp. 5523-5537.
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Golovanov I. S., Malykhin R. S., Lesnikov V. K., Nelyubina Y. V., Novikov V. V., Frolov K. V., Stadnichenko A., Tretyakov E., Ioffe S. L., Sukhorukov A. Yu. Revealing the Structure of Transition Metal Complexes of Formaldoxime // Inorganic Chemistry. 2021. Vol. 60. No. 8. pp. 5523-5537.
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TY - JOUR
DO - 10.1021/acs.inorgchem.0c03362
UR - https://doi.org/10.1021%2Facs.inorgchem.0c03362
TI - Revealing the Structure of Transition Metal Complexes of Formaldoxime
T2 - Inorganic Chemistry
AU - Lesnikov, Vladislav K
AU - Frolov, Kirill V.
AU - Golovanov, Ivan S
AU - Novikov, Valentin V
AU - Tretyakov, Evgeny
AU - Sukhorukov, Alexey Yu
AU - Malykhin, Roman S
AU - Nelyubina, Yulia V.
AU - Stadnichenko, Andrey
AU - Ioffe, Sema L.
PY - 2021
DA - 2021/04/07 00:00:00
PB - American Chemical Society (ACS)
SP - 5523-5537
IS - 8
VL - 60
SN - 0020-1669
SN - 1520-510X
ER -
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@article{2021_Golovanov,
author = {Vladislav K Lesnikov and Kirill V. Frolov and Ivan S Golovanov and Valentin V Novikov and Evgeny Tretyakov and Alexey Yu Sukhorukov and Roman S Malykhin and Yulia V. Nelyubina and Andrey Stadnichenko and Sema L. Ioffe},
title = {Revealing the Structure of Transition Metal Complexes of Formaldoxime},
journal = {Inorganic Chemistry},
year = {2021},
volume = {60},
publisher = {American Chemical Society (ACS)},
month = {apr},
url = {https://doi.org/10.1021%2Facs.inorgchem.0c03362},
number = {8},
pages = {5523--5537},
doi = {10.1021/acs.inorgchem.0c03362}
}
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Golovanov, Ivan S., et al. “Revealing the Structure of Transition Metal Complexes of Formaldoxime.” Inorganic Chemistry, vol. 60, no. 8, Apr. 2021, pp. 5523-5537. https://doi.org/10.1021%2Facs.inorgchem.0c03362.