Two Discoveries in One Crystal: σ-Type Oxime Radical as an Unforeseen Building Block in Molecular Magnetics and Its Spatial Structure

Two Discoveries in One Crystal: σ-Type Oxime Radical as an Unforeseen Building Block in Molecular Magnetics and Its Spatial Structure Full article

Journal

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

Output data

Year: 2023, Volume: 62, Number: 28, Pages: 10965-10972 Pages count : 8 DOI: 10.1021/acs.inorgchem.3c00947

Authors

Budnikov Alexander S. ¹ , Krylov Igor B. ¹ , Ushakov Ivan E. ² , Subbotina Irina R. ¹ , Monin Fedor K. ¹ , Nikishin Gennady I. ¹ , Efimov Nikolay N. ³ , Gorbunov Dmitry E. ⁴ , Gritsan Nina P. ⁴ , Tretyakov Evgeny V. ¹ , Yu Bing ⁵ , Terent’ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation
2	A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 28 Vavilova Str., Moscow 119991, Russian Federation
3	N. S. Kurnakov Institute of General and Inorganic Chemistry, Leninsky Prospect 31, Moscow 119991, Russia
4	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russian Federation
5	Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001, China

In the present work, the study of the unusual interaction between copper hexafluoroacetylacetonate and the diacetyliminoxyl radical resulted in two discoveries from different fields: the determination of the oxime radical spatial structure and the introduction of an oxime radical into the field of molecular magnetic material design. Oxime radicals are key plausible intermediates in the processes of oxidative CH-functionalization and in the synthesis of functionalized isoxazolines from oximes. Due to the lack of X-ray diffraction data for oxime radicals, the knowledge about their structure is based mainly on indirect approaches, spectroscopic methods (electron paramagnetic resonance and IR), and quantum chemical calculations. The structure of the oxime radical was determined for the first time by stabilizing the diacetyliminoxyl radical in the form of its complex with copper (II) hexafluoroacetylacetonate (Cu(hfac)2), followed by single-crystal X-ray diffraction analysis. Although oxime radicals are known to undergo oxidative coupling with acetylacetonate ligands in transition-metal complexes, a complex is formed with intact hfac ligands. X-ray diffraction studies have shown that the oxime radical is coordinated with copper ions through the oxygen atoms of the carbonyl groups without the direct involvement of the C═N–O• radical moiety. The structure of the coordinated diacetyliminoxyl is in good agreement with the density functional theory (DFT) prediction for free diacetyliminoxyl due to the very weak interaction of the radical molecule with copper ions. Remarkably, both weak ferromagnetic and antiferromagnetic interactions between Cu (II) and oxime radicals have been revealed by modeling the temperature dependence of magnetic susceptibility and confirmed by DFT calculations, rendering diacetyliminoxyl a promising building block for the design of molecular magnets.

Budnikov A.S. , Krylov I.B. , Ushakov I.E. , Subbotina I.R. , Monin F.K. , Nikishin G.I. , Efimov N.N. , Gorbunov D.E. , Gritsan N.P. , Tretyakov E.V. , Yu B. , Terent’ev A.O.
Two Discoveries in One Crystal: σ-Type Oxime Radical as an Unforeseen Building Block in Molecular Magnetics and Its Spatial Structure
Inorganic Chemistry. 2023. V.62. N28. P.10965-10972. DOI: 10.1021/acs.inorgchem.3c00947 WOS Scopus OpenAlex

Web of science:	WOS:001018795100001
Scopus:	2-s2.0-85164686966
OpenAlex:	W4382931369

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