The synthesis of binuclear half-open 1,1′-biferrocene: redox behavior and an interpretation of the 57Fe Mössbauer data

Dong, Tungalag; Chang, Chung-Kay; Cheng, Ching-Hung

doi:10.1016/s0022-328x(99)00270-3

Cited by 4 publications

(1 citation statement)

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“…The electronic interaction between metal centers at a defined distance 36 has raised considerable interest among chemists, e.g., in the question of electron transfer through peptides 37-42 or the stacked bases of helical DNA. − The square wave voltammogram of 7 is not significantly different from the sum of the square wave voltammograms of 3a and 6, with its peak potential comparable to that of 3a and 6 and a width at a half-potential w 1/2 of 230 mV (compared to a w 1/2 of 118 and 119 mV for 3a and 6 , respectively). This result does not support a direct electronic interaction between the ferrocene centers . Indeed, molecular modeling suggests a minimum distance between the metal centers of about 10 Å even in a helical structure which places the metal centers in proximity.…”

Section: Spectroscopic Characterization and Discussionmentioning

confidence: 65%

Chiral Ferrocene Amines Derived from Amino Acids and Peptides: Synthesis, Solution and X-ray Crystal Structures and Electrochemical Investigations

Hess

Sehnert²,

Weyhermüller³

et al. 2000

Inorg. Chem.

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For the recognition of all but the simplest naturally occurring molecules, electrochemical sensors based on ferrocene will certainly require chiral centers. To advance the necessary chemistry, this work describes the synthesis and properties of ferrocene derivatives of enantiomerically pure amino acids, peptides, and other chiral amines. Ferrocene aldehyde is condensed with amino acid esters to yield the corresponding Schiff bases 2, which are reduced by NaBH4 in methanol to the ferrocene methyl amino acids 3. An X-ray single-crystal analysis was carried out on the phenylalanine derivative 3a (monoclinic space group P2(1), a = 10.301(1) A, b = 9.647(1) A, c = 18.479(2) A, beta = 102.98(2) degrees, Z = 4). Further peptide chemistry at the C terminus proceeds smoothly as demonstrated by the synthesis of the ferrocene labeled dipeptide Fc-CH2-Phe-Gly-OCH3 5 (Fc = ferrocenyl ((eta-C5H4)Fe(eta-C5H5))). We also report the synthesis of the C,N-bis-ferrocene labeled tripeptide Phe-Ala-Leu and its electrochemical characterization. Starting from the enantiomerically pure ferrocene derivative 9, which was synthesized from ferrocene aldehyde and L-1-amino-ethylbenzene, two diastereomers 10 were obtained by peptide coupling with N-Boc protected D- and L-alanine. There was, however, only very little diastereomeric induction if 0.5 equiv of a racemic mixture of alanine were used. This suggests that amino acid activation rather than coupling is the rate-determining step. A combination of NOESY (nuclear Overhauser effect spectroscopy) spectra and molecular modeling furnished detailed insights into the solution structures of 3, 9, and 10 and was used to rationalize their different reactivity.

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