The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Inkpen, Michael; Du, Shuoren; Hildebrand, Mariana; White, Andrew; Harrison, Nicholas; Albrecht, Tim; Long, Nicholas; Long, Nicholas

doi:10.1149/ma2016-02/45/3316

Cited by 4 publications

(8 citation statements)

References 7 publications

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“…Long et al, 18 by studying the series of the four monosubstituted and the four disubstituted FcX n compounds (X = F, Cl, Br, I; n = 1, 2), also observed that the effects of Br and Cl were similar. The behavior of the easily oxidized F-substituted derivatives made these authors note that the redox trend could not be simply explained by invoking the electronegativity of the substituents.…”

Section: ■ Results and Discussionmentioning

confidence: 93%

Synthetic Route to 1,1′,2,2′-Tetraiodoferrocene That Avoids Isomerization and the Electrochemistry of Some Tetrahaloferrocenes

et al. 2021

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An efficient synthesis of 1,1′,2,2′-tetraiodoferrocene is described that uses 1,1′,2,2′-tetrakis(tri-n-butylstannyl)ferrocene as a key intermediate in its synthesis. In an attempt to examine the stepwise mechanism, the reaction of the tetratin-substituted ferrocene 1,1′,2,2′-tetrakis(tri-n-butylstannyl)ferrocene with iodine was monitored by 1H NMR and a series of coexisting intermediate compounds such as 1,1′-bis(tri-n-butylstannyl)-2,2′-diodoferrocene were observed. The crystal structure of 1,1′,2,2′-tetraiodoferrocene has been determined, and it is compared with the structure of the previously reported 1,1′,2,2′-tetrabromoferrocene and 1,2,4,1′-tetraiodoferrocene. The comparative electrochemistry of 1,1′,2,2′-tetrachloroferrocene, 1,1′,2,2′-tetrabromoferrocene, and 1,1′,2,2′-tetraiodoferrocene is described. The crystal structure of 1,2,1′-triiodoferrocene is also reported for comparative use to illustrate the scope of the synthetic method.

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Section: ■ Results and Discussionmentioning

confidence: 93%

Synthetic Route to 1,1′,2,2′-Tetraiodoferrocene That Avoids Isomerization and the Electrochemistry of Some Tetrahaloferrocenes

et al. 2021

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“…The introduction of a chlorine instead of a methyl group increased the redox potential by 0.21 V (compound 8a), slightly more than the +0.16 V anticipated from the work of Albrecht and Long. 151 Probably due to the effect of the trimethylsilyl substituent, all three ferrocenes 5c, 8a and 10 underwent a oneelectron totally reversible oxidation. While we recorded no evolution of the E 1/2 value between ferrocenes 5c and 10, the expected effect of a methyl substituent (-0.05V) 145 was observed between the ferrocenes 3e and 11.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

“…The introduction of iodine with the compound 12 resulted in a smaller increase of the redox potential than expected (+0.11 V vs +0.15 V). 151 Upon the introduction of the dimethylaminomethyl substituent (compound 13), an irreversible oxidation process was observed at +0.64 V, which was attributed to the oxidation of the tertiary amine into an iminium (Figure 6). 152 The latter also raised the redox potential of the ferrocene core by +0.21 V. 152 In this series of fluorinated ferrocenesulfonyl fluorides, it appeared that the evolution of the redox potential does not follow a purely additive effect of each substituent.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

“…Indeed, many other factors such as orbitals ordering, changes in hybridization and frontier orbital composition, through-space interaction between the metal and the substituents as well as electrostatic repulsion between the metal and the Cp ring orbitals need to be considered. 147,151,154 Therefore, a better understanding of the substituent effect on the redox potential of a hetero polysubstituted ferrocene would require a dedicated study, which falls out the scope of this work.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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Exploring the boundaries of ferrocenesulfonyl fluoride chemistry

Erb

Hurvois

Halauko

et al. 2022

Inorg. Chem. Front.

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“…Still, nearly 1 V has been tuned on the same platform. 25,26 All of these complexes are positively charged, e.g., [Fe(C 5 Cl 5 ) 2 ] + or [Ru(bpy) 3 ] 2+ . Indeed, despite the fact that ligands are either negative or neutral, very few chemically stable and robust anionic complexes are available ready for E°tuning.…”

Section: ■ Introductionmentioning

confidence: 99%

1.3 V Inorganic Sequential Redox Chain with an All-Anionic Couple 1–/2– in a Single Framework

et al. 2021

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The relatively low symmetry of [3,3′-Co(1,2-C 2 B 9 H 11 ) 2 ] − ([ 1 ] − ), along with the high number of available substitution sites, 18 on the boron atoms and 4 on the carbon atoms, allows a fairly regioselective and stepwise chlorination of the platform and therefore a very controlled tuning of the electrochemical potential tuning. This is not so easily found in other systems, e.g., ferrocene. In this work, we show how a single platform with boron and carbon in the ligand, and only cobalt can produce a tuning of potentials in a stepwise manner in the 1.3 V range. The platform used is made of two icosahedra sharing one vertex. The E 1/2 tuning has been achieved from [ 1 ] − by sequential chlorination, which has given potentials whose values increase sequentially and linearly with the number of chloro groups in the platform. [ Cl 8 -1 ] − , [ Cl 10 -1 ] − , and [ Cl 12 -1 ] − have been obtained, which are added to the existing [ Cl-1 ] − , [ Cl 2 -1 ] − , [ Cl 4 -1 ] − , and [ Cl 6 -1 ] − described earlier to give the 1.3 V range. It is envisaged to extend this range also sequentially by changing the metal from cobalt to iron. The last successful synthesis of the highest chlorinated derivatives of cobaltabis(dicarbollide) dates back to 1982, and since then, no more advances have occurred toward more substituted metallacarborane chlorinated compounds. [ Cl 8 -1 ] − , [ Cl 10 -1 ] − , and [ Cl 12 -1 ] − are made with an easy and fast method. The key point of the reaction is the use of the protonated form of [Co(C 2 B 9 H 11 ) 2 ] − , as a starting material, and the use of sulfuryl chloride, a less hazardous and easier to use chlorinating agent. In addition, we present a complete, spectroscopic, crystallographic, and electrochemical characterization, together with a study of the influence of the chlorination position in the electrochemical properties.

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The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

Cited by 4 publications

References 7 publications

Synthetic Route to 1,1′,2,2′-Tetraiodoferrocene That Avoids Isomerization and the Electrochemistry of Some Tetrahaloferrocenes

Synthetic Route to 1,1′,2,2′-Tetraiodoferrocene That Avoids Isomerization and the Electrochemistry of Some Tetrahaloferrocenes

Exploring the boundaries of ferrocenesulfonyl fluoride chemistry

1.3 V Inorganic Sequential Redox Chain with an All-Anionic Couple 1–/2– in a Single Framework

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