Phosphination of ferrocenium cation with aminophosphines


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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.

作者简介

A. Chamkin

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

V. Krivykh

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

N. Shtel’tser

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

O. Semeikin

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

F. Dolgushin

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

N. Ustynyuk

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: ustynyuk@ineos.ac.ru
俄罗斯联邦, 28 ul. Vavilova, Moscow, 119991

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