Synthesis and photochemical study of tricarbonyl and dicarbonyl derivatives of 3-cymantrenylalkylisothioureas

Telegina, Lyudmila N.; Стрелкова, Т. В.; Ezernitskaya, M. G.; Medvedev, Michael G.; Kelbysheva, E. S.

doi:10.1016/j.jorganchem.2020.121465

Cited by 3 publications

(3 citation statements)

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“…The frequencies are close to those described for dicarbonyl chelates with the MnÀ S bond. [11] Thus, the photolysis of tricarbonyl complexes 1-2 results in the formation of chelates 4-5 (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

Hemilabile Properties of Sulfur‐Containing Cymantrene Derivatives

et al. 2021

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Sulfur-containing cymantrene derivatives having one or two organometallic moieties were studied by NMR, IR, UV/Vis spectroscopic methods and CVA under irradiation conditions. Photolysis of compounds 1-3 leads to the formation of rare 4membered chelates 4, 5 and 8. In the presence of external ligand (L), dissociation of the MnÀ S bond occurred to form new dicarbonyl complexes with the MnÀ L bond, which demonstrates the hemilabile character of the chelates obtained. The results were confirmed by DFT calculations. CVA method showed manganese oxidation potential value increased in the case of dicarbonyls (1313 mV for 4) as compared to that of tricarbonyls (1067 mV for 1).

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Section: Resultsmentioning

confidence: 99%

Hemilabile Properties of Sulfur‐Containing Cymantrene Derivatives

et al. 2021

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“…Cymantrenes’ modus operandi upon excitation consists in releasing one carbonyl with the formation of a 16‐electron Mn complex and then filling the emerged Mn valence with whatever is present nearby before proceeding to the thermodynamic sink [32–34] …”

Section: Introductionmentioning

confidence: 99%

“…[31] Cymantrenes' modus operandi upon excitation consists in releasing one carbonyl with the formation of a 16-electron Mn complex and then filling the emerged Mn valence with whatever is present nearby before proceeding to the thermodynamic sink. [32][33][34] Previously we have studied [35] the alkylation reaction of methyl-and styrylquinazolin-4-ones with bromomethylcymantrene in the presence of sodium hydride, which led to N-substituted products containing quinazolinone and cymantrene fragments within one molecule exhibiting notable photochromic and fluorescent properties. [36] At the same time, identical alkylation of quinazolinone 1 (Scheme 1, see Experimental Section for details) led to the formation of a mixture of products of 4O-and 3 N-substituted quinazolines (3 and 4) in a ratio of approximately 1 : 1.…”

Section: Introductionmentioning

confidence: 99%

CO‐Preserving Photoinduced Transfer of Cymantrenyl Moiety: a Tandem Experimental and Computational Investigation

Chaliy

Kelbysheva

Ezernitskaya

et al. 2023

Chemistry A European J

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Cyclopentadienyl manganese tricarbonyl (cymantrene) is known to undergo photochemical reactions by releasing one of its CO ligands. Here we present the first example of a photorearrangement of a cymantrenylmethyl fragment, where it retains all its three CO ligands. A tandem experimental and DFT (density functional theory)-based computational investigation allows us to explain this unexpected behavior: the rearrangement, indeed, begins with the release of one CO ligand, but cage effect of the solvent captures this CO molecule, allowing it to rapidly reattach once the rearrangement takes place.

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