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Phosphination of ferrocenium cation with aminophosphines

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Abstract

Ferrocenium hexafluorophosphate reacts with aminophosphines P(NEt2)3, PhP(NEt2)2, Ph2P(NEt2), CyP(NEt2)2, and Pri2P(NEt2) to form ferrocenylphosphonium salts [(C5H5)-Fe(C5H4PRR′R″)](PF6), ferrocene, and [HPRR′R″](PF6). The theoretical analysis of the reactions (M06-L/6-311++G(d,p)) showed that these reactions involve a sequence of the following steps: the addition of phosphine to the cyclopentadienyl ring, the oxidation of the initial adduct by the starting ferrocenium to give a dicationic η4-phosphocyclopentadiene complex with an agostic \(C_{sp^{3}}-H\rightarrow{Fe}\) bond, and the deprotonation of this bond to form ferrocenylphosphonium salts. The resulting ferrocenylphosphonium salts are resistant to alcoholysis and do not react with carbon disulfide.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    A. A. Chamkin, V. V. Krivykh, N. A. Shtel’tser, O. V. Semeikin, F. M. Dolgushin & N. A. Ustynyuk

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  1. A. A. Chamkin
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  2. V. V. Krivykh
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  3. N. A. Shtel’tser
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  4. O. V. Semeikin
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  5. F. M. Dolgushin
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  6. N. A. Ustynyuk
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Correspondence to N. A. Ustynyuk.

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Chamkin, A.A., Krivykh, V.V., Shtel’tser, N.A. et al. Phosphination of ferrocenium cation with aminophosphines. Russ Chem Bull 68, 532–539 (2019). https://doi.org/10.1007/s11172-019-2450-2

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  • DOI: https://doi.org/10.1007/s11172-019-2450-2

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