Phosphination of ferrocenium cation with aminophosphines

• Published in: Russian chemical bulletin Vol. 68; no. 3; pp. 532 - 539
• Main Authors: Chamkin, A. A., Krivykh, V. V., Shtel’tser, N. A., Semeikin, O. V., Dolgushin, F. M., Ustynyuk, N. A.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01-03-2019; Springer Nature B.V
• Subjects: Carbon disulfide; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Article; Inorganic Chemistry; Organic Chemistry; Oxidation; aminophosphines; oxidative nucleophilic substitution; ferrocenium; ferrocenylphosphonium salts
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-019-2450-2

Ferrocenium hexafluorophosphate reacts with aminophosphines P(NEt
2
)
3
, PhP(NEt
2
)
2
, Ph
2
P(NEt
2
), CyP(NEt
2
)
2
, and Pr
i
2
P(NEt
2
) to form ferrocenylphosphonium salts [(C
5
H
5
)-Fe(C
5
H
4
PRR′R″)](PF
6
), ferrocene, and [HPRR′R″](PF
6
). 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 η
4
-phosphocyclopentadiene complex with an agostic
C
s
p
3
−
H
→
F
e
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.