57Fe-Mössbauer and13C-CP-MAS NMR spectroscopic studies of reaction products of ferrocenylruthenocene with Lewis acids

Watanabe, Masanobu; Masuda, Yuichi; Motoyama, Izumi; Sano, Hirotoshi

doi:10.1007/bf02049116

Cited by 6 publications

(2 citation statements)

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“…Depending upon the reaction conditions (at low temperatures or in apolar solvents), the precipitation of dimers (oligomers) of complexes A and B may occur. In fact, the red complexes of ferrocene and its derivatives with various mercuric halides have been isolated and studied by various techniques. − In alcoholic solvents, the precipitation of dimers of complexes A and B or compounds of other stoichiometry is disfavored and the mercuration proceeds as expected. It is apparent, however, that the solubility of ferrocene−HgX 2 adducts depends on both the solvent and the nature of X.…”

Section: Resultsmentioning

confidence: 99%

“…The interaction of various mercury(II) compounds with ferrocene has been the subject of a number of publications. Although the precise structure of ferrocene−mercuric salt adducts is yet to be resolved, the presence of an iron−mercury bond has been detected by infrared, Mössbauer, 3i,, solid state 13 C NMR, and ultraviolet spectroscopy . Indeed, the kinetic evaluation of the acetoxymercuration of ferrocene in acetic acid seemed to indicate the rapid formation of a related 1:1 adduct of ferrocene:mercuric acetate ( A , E = Hg(OCOCH 3 ) 2 ) followed by the rate determining formation of the carbon−mercury bond (endo attack) 3h…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of Mercuration of Ferrocene: General Treatment of Electrophilic Substitution of Ferrocene Derivatives

Cunningham¹

1997

Organometallics

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The mercuration of (pentadeuteriocyclopentadienyl)cyclopentadienyliron(II), 1, occurs preferentially at the C5H5 ring. The ratio of C5H5:C5D5 attack ranges from 5.2−6.5, depending upon the mercurating agent employed. In contrast to the Friedel−Crafts acetylation of 1, mercuration does not give rise to intramolecular interannular proton transfers. Under certain conditions, a complex, 6, can be isolated that contains both carbon−mercury and iron−mercury bonds. Taking these facts into account, a mechanism for the mercuration of ferrocene is proposed whereby precomplexation of the mercurating agent to the iron atom precedes the rate determining formation of the carbon−mercury bond with concomitant loss of H+. Combined with our previous work concerning the acetylation and proton exchange of ferrocene, this study allows the formulation of a general mechanism of electrophilic substitution of ferrocene, based on the reactivity of the electrophile and the basicity of the iron atom of the resulting ferrocene product.

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Section: Resultsmentioning

confidence: 99%