12180-80-2Relevant articles and documents
Woodward, R. B.,Rosenblum, M.,Whiting, M. C.
, p. 3458 - 3459 (1952)
Tomassetti, M.,Curini, R.,D'Ascenzo, G.,Ortaggi, G.
, p. 333 - 342 (1981)
Acceptor-substituted ferrocenium salts as strong, single-electron oxidants: Synthesis, electrochemistry, theoretical investigations, and initial synthetic application
Khobragade, Dushant A.,Mahamulkar, Shraddha G.,Pospí?il, Lubomír,Císa?ová, Ivana,Rulí?ek, Lubomír,Jahn, Ullrich
supporting information, p. 12267 - 12277 (2012/11/14)
A series of mono- and 1,1'-diheteroatom-substituted ferrocene derivatives as well as acylated ferrocenes was prepared efficiently by a unified strategy that consists of selective mono- and 1,1'-dilithiation reactions and subsequent coupling with carbon, phosphorus, sulfur and halogen electrophiles. Chemical oxidation of the ferrocene derivatives by benzoquinone, 2,3-dichloro-5,6- dicyanobenzoquinone, AgPF6, or 2,2,6,6-tetramethyl-1-oxopiperidinium hexafluorophosphate provided the corresponding ferrocenium salts. The redox potentials of the synthesized ferrocenes were determined by cyclic voltammetry, and it was observed that all new ferrocenium salts have stronger oxidizing properties than standard ferrocenium hexafluorophosphate. An initial application of selected derivatives in an oxidative bicyclization revealed that they mediate the transformation under considerably milder conditions than ferrocenium hexafluorophosphate. Quantum chemical calculations of the reduction potentials of the substituted ferrocenium ions were carried out by using a standard thermodynamic cycle that involved the gas-phase energetics and solvation energies of the contributing species. A remarkable agreement between theory and experiment was found: the mean average deviation amounted to only 0.030-V and the maximum deviation to 0.1-V. This enabled the analysis of various physical contributions to the computed reduction potentials of these ferrocene derivatives, thereby providing insight into their electronic structure and physicochemical properties. Copyright
Efficient regio- and diastereo-controlled synthesis of 1,1′- and 1,1′,2,2′-functionalised ferrocenes and the formation of 2-oxa[3]ferrocenophanes
Carroll, Michael A.,White, Andrew J.P.,Widdowson, David A.,Williams, David J.
, p. 1551 - 1557 (2008/10/08)
The synthesis of a C2 symmetric 1,1′ ,2,2′-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1′-bis(hydroxymethyl)ferrocenes and 1,1′-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.
