Multi-functionalized ferrocenes: - Synthesis and characterization

Alexander Hildebrandt, Khaled Al Khalyfeh, Dieter Schaarschmidt, Marcus Korb

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Ferrocenes with up to four formyl functionalities have been synthesized by selective one-or two-fold ortho-lithiation of 1,1'-di(1,3-dioxan-2-yl)ferrocene followed by the reaction with dimethylformamide. Subsequent deprotection afforded tri- and tetraformyl-ferrocene in good yields. Wittig reactions convert the aldehydes to tri-and tetravinyl-ferrocene. The structures of three formyl-ferrocenes in the solid-state have been determined by single crystal X-ray diffraction. In two of the structures the ferrocene moieties form 1D chains by parallel displaced p-interactions with Cp center dot center dot center dot Cp distances as short as 3.21 angstrom. Electrochemical measurements (CV) demonstrated an irreversible behavior of the electron-poor multi-formyl ferrocenes. Reducing the measurement temperature down to -40 degrees C and the usage of [(NBu4)-Bu-n][B(C6F5)(4)] prevents side reactions and hence reversible redox-processes could be obtained. It was found that the number of formyl functionalities correlates with the ferrocenyl's redox potential in a strictly linear fashion. (C) 2015 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)87-94
Number of pages8
JournalJournal of Organometallic Chemistry
Volume804
DOIs
Publication statusPublished - 15 Feb 2016
Externally publishedYes

Cite this

Hildebrandt, Alexander ; Al Khalyfeh, Khaled ; Schaarschmidt, Dieter ; Korb, Marcus. / Multi-functionalized ferrocenes : - Synthesis and characterization. In: Journal of Organometallic Chemistry. 2016 ; Vol. 804. pp. 87-94.
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Multi-functionalized ferrocenes : - Synthesis and characterization. / Hildebrandt, Alexander; Al Khalyfeh, Khaled; Schaarschmidt, Dieter; Korb, Marcus.

In: Journal of Organometallic Chemistry, Vol. 804, 15.02.2016, p. 87-94.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Multi-functionalized ferrocenes

T2 - - Synthesis and characterization

AU - Hildebrandt, Alexander

AU - Al Khalyfeh, Khaled

AU - Schaarschmidt, Dieter

AU - Korb, Marcus

PY - 2016/2/15

Y1 - 2016/2/15

N2 - Ferrocenes with up to four formyl functionalities have been synthesized by selective one-or two-fold ortho-lithiation of 1,1'-di(1,3-dioxan-2-yl)ferrocene followed by the reaction with dimethylformamide. Subsequent deprotection afforded tri- and tetraformyl-ferrocene in good yields. Wittig reactions convert the aldehydes to tri-and tetravinyl-ferrocene. The structures of three formyl-ferrocenes in the solid-state have been determined by single crystal X-ray diffraction. In two of the structures the ferrocene moieties form 1D chains by parallel displaced p-interactions with Cp center dot center dot center dot Cp distances as short as 3.21 angstrom. Electrochemical measurements (CV) demonstrated an irreversible behavior of the electron-poor multi-formyl ferrocenes. Reducing the measurement temperature down to -40 degrees C and the usage of [(NBu4)-Bu-n][B(C6F5)(4)] prevents side reactions and hence reversible redox-processes could be obtained. It was found that the number of formyl functionalities correlates with the ferrocenyl's redox potential in a strictly linear fashion. (C) 2015 Elsevier B.V. All rights reserved.

AB - Ferrocenes with up to four formyl functionalities have been synthesized by selective one-or two-fold ortho-lithiation of 1,1'-di(1,3-dioxan-2-yl)ferrocene followed by the reaction with dimethylformamide. Subsequent deprotection afforded tri- and tetraformyl-ferrocene in good yields. Wittig reactions convert the aldehydes to tri-and tetravinyl-ferrocene. The structures of three formyl-ferrocenes in the solid-state have been determined by single crystal X-ray diffraction. In two of the structures the ferrocene moieties form 1D chains by parallel displaced p-interactions with Cp center dot center dot center dot Cp distances as short as 3.21 angstrom. Electrochemical measurements (CV) demonstrated an irreversible behavior of the electron-poor multi-formyl ferrocenes. Reducing the measurement temperature down to -40 degrees C and the usage of [(NBu4)-Bu-n][B(C6F5)(4)] prevents side reactions and hence reversible redox-processes could be obtained. It was found that the number of formyl functionalities correlates with the ferrocenyl's redox potential in a strictly linear fashion. (C) 2015 Elsevier B.V. All rights reserved.

KW - Electrochemistry

KW - Formyl-ferrocene

KW - Vinyl-ferrocene

KW - Wittig reaction

KW - X-ray structure

KW - ONE-ELECTRON OXIDATION

KW - CONTAINING POLYMERS

KW - SOLID-STATE

KW - ASYMMETRIC CATALYSIS

KW - NONAQUEOUS SOLVENTS

KW - DERIVATIVES

KW - ELECTROCHEMISTRY

KW - COMPLEXES

KW - BATTERIES

KW - CRYSTAL

U2 - 10.1016/j.jorganchem.2015.12.027

DO - 10.1016/j.jorganchem.2015.12.027

M3 - Article

VL - 804

SP - 87

EP - 94

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -