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Formation of Carbocationic σ-Alkyl Ni(I) Complexes in the Catalytic System Ni(PPh3)4+ BF3· OEt2. Ionic Coordination Transformations of Unsaturated Hydrocarbons

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Abstract

The reactions of the individual cationic complex [(PPh3)3Ni]BF4with unsaturated hydrocarbons (ethene, propene, and styrene), as well as the reaction of the σ-alkyl Ni(I) complex (PPh3)2Ni–CH(COOC2H5)2(obtained in situ) with ethene, were studied using EPR, UV, and NMR spectroscopy. It was found that stable dimeric carbocationic σ-alkyl Ni(I) complexes are intermediates in the reactions of unsaturated hydrocarbons with cationic Ni(I) complexes. The transformations of unsaturated hydrocarbons on cationic Ni(I) complexes were explained in terms of an experimentally justified ionic coordination mechanism. A stable mononuclear Ni(I) complex with a Ni–C σ-bond was synthesized and characterized using EPR. An organonickel(I) complex with π- and σ-bonded carbon atoms was identified using EPR and NMR methods.

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Authors and Affiliations

  1. Irkutsk State University, ul. Lermontova 126, Irkutsk, 664033, Russia

    V. V. Saraev, P. B. Kraikivskii, S. N. Zelinskii, G. V. Ratovskii, V. S. Tkach & F. K. Shmidt

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  1. V. V. Saraev
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  2. P. B. Kraikivskii
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  3. S. N. Zelinskii
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  4. G. V. Ratovskii
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  5. V. S. Tkach
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  6. F. K. Shmidt
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Saraev, V.V., Kraikivskii, P.B., Zelinskii, S.N. et al. Formation of Carbocationic σ-Alkyl Ni(I) Complexes in the Catalytic System Ni(PPh3)4+ BF3· OEt2. Ionic Coordination Transformations of Unsaturated Hydrocarbons. Russian Journal of Coordination Chemistry 27, 757–762 (2001). https://doi.org/10.1023/A:1012509802979

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  • DOI: https://doi.org/10.1023/A:1012509802979

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