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Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions

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Abstract

Such ketazines as azines of acetophenone and its substituted derivatives (p-F, m-Cl, p-I, p-Me, p-OMe), acetone, dibenzyl ketone, propiophenone, and indan-2-one were studied in the reaction with phosphorus(ɪɪɪ) chloride. The possibility of the formation of 1,4-dichloro-3a,6a-diaza-1,4-diphosphapentalenes is largely determined by the nature of the starting ketazine. Diazadiphosphapentalene dichlorides exist in solution as a mixture of cis- and trans-isomers, but crystallize exclusively as 1,4-trans-isomers. Reduction of 3a,6a-diaza-1,4-diphosphapentalene dichlorides with manganese in tetrahydrofuran gives the corresponding diazadiphosphapentalenes in 52–63% yield. The electrochemical properties of the obtained compounds were studied by cyclic voltammetry. Two dichlorides of 3a,6a-diaza-1,4-diphosphapentalenes were found to have anomalous oxidation potentials of 0.29 and 0.13 V related to the formation of free diazadiphosphapentalenes in solution as a result of disproportionation under the influence of the donor solvent, which was confirmed by 31P NMR spectroscopy, electronic absorption spectroscopy, and independent syntheses.

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Authors and Affiliations

  1. G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 ul. Tropinina, 603950, Nizhny Novgorod, Russian Federation

    Yu. S. Panova, A. V. Khristolyubova, V. V. Sushev, N. V. Zolotareva, M. D. Grishin, E. V. Baranov, G. K. Fukin & A. N. Kornev

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  1. Yu. S. Panova
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  2. A. V. Khristolyubova
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  3. V. V. Sushev
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  4. N. V. Zolotareva
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  5. M. D. Grishin
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  6. E. V. Baranov
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  7. G. K. Fukin
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  8. A. N. Kornev
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Correspondence to A. N. Kornev.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1973–1986, October, 2021.

This work was financially supported by the Russian Science Foundation (Project No. 19-13-00400) and was carried out using scientific equipment of the Center for Collective Use “Analytical Center of IOMC RAS” in the G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences within the framework of the federal target program “Research and development in priority areas of development of the scientific and technological complex of Russia for 2014–2020” (unique project identifier RFMEFI62120X0040).

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Panova, Y.S., Khristolyubova, A.V., Sushev, V.V. et al. Synthesis of 3a,6a-diaza-1,4-diphosphapentalenes and their halogen derivatives. Specific features of the structure and behavior in solutions. Russ Chem Bull 70, 1973–1986 (2021). https://doi.org/10.1007/s11172-021-3305-1

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