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Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

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Abstract

The interaction of labeled dinitrogen complexescis-(Me2PhP)4Mo(15N2)2 andtrans-(dppe)2W(15N2)2 with non-labeled nitronium and nitrosonium fluoroborates,14NO2BF4 and14NOBF4, in sulfolane at room temperature in the presence of H2SO4 results in rapid formation of labeled nitrous and nitric oxides (15N14NO,15NO), as well as15N14N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2−) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2−) complexes, (Me2PhP)3Mo(15N2H2)Cl2 and (dppe)2W(15N2H2)Cl2, are capable of forming15N14NO,15NO, and15N14N under the action of14NO2BF4 and14NOBF4 in the absence of an acid.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    V. S. Lenenko, V. B. Shur & M. E. Vol'pin

  2. Institute of Organic Chemistry, University of Leipzig, P 2 Permoserstr. 15, D-04303, Leipzig, Germany

    P. Kränke & M. Wahren

Authors
  1. V. S. Lenenko
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  2. P. Kränke
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  3. M. Wahren
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  4. V. B. Shur
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  5. M. E. Vol'pin
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.

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Lenenko, V.S., Kränke, P., Wahren, M. et al. Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides. Russ Chem Bull 44, 1293–1299 (1995). https://doi.org/10.1007/BF00700907

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  • DOI: https://doi.org/10.1007/BF00700907

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