A triply-bridged dinuclear tris(bipyridine)iron(II) complex: synthesis and electrochemical and structural studies

Serr, Barbara R.; Andersen, K. A.; Elliott, C. Michael; Anderson, Oren P.

doi:10.1021/ic00297a032

Cited by 116 publications

(66 citation statements)

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“…The electrochemical changes upon addition of the above-mentioned set of metal cations to the receptor 3 was also investigated by using DPV to explore the metal recognition process more accurately. [16] Indeed, the study indicates that this receptor behaves as a selective electrochemical sensor for Zn 2 + in CH 2 Cl 2 /CH 3 CN (4:1). The addition of increasing amounts of Zn 2 + to the electrochemical solution (up to 2.25 equiv) of receptor 3 caused the partial disappearance of the wave at À0.06 V and the simultaneous appearance of a new wave at 0.02 V. However, the second wave of the free receptor, at E1 = 2 = 0.46 V, does not suffer any perceptible change during the titration.…”

Section: Resultsmentioning

confidence: 86%

Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing

Otón

Ratera

Espinosa

et al. 2010

Chemistry A European J

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The synthesis, electrochemical, optical, and cation-sensing properties of [2.2]ferrocenophanes, in which the two ferrocene subunits are linked through two aldiminic or iminophosphorane moieties, are reported. The new compounds show remarkably selective cation-sensing properties due to the presence of redox-active units (ferrocene) and aza-unsaturated functionalities that are able to act as putative cation-binding sites. In this structural motif, the aldimine groups act as a highly selective binding site for Zn(2+) cations, whereas the iminophosphorane bridges display an unusually strong binding affinity towards Li(+) cations, which could be explained by an additional LiFe interaction. The X-ray structure of the complex 4Li(+) as well as detailed NMR spectroscopic studies, both in solution and in the solid state, support this assessment. Experimental data and conclusions about the cation-sensing capabilities of this family of compounds are supported by DFT calculations.

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Section: Resultsmentioning

confidence: 86%

Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing

Otón

Ratera

Espinosa

et al. 2010

Chemistry A European J

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“…We selected the [Fe 2 (3) 3 ] 4 helicate 4Ðreported by Elliott et al in 1988Ðfor its ease of preparation from readily accessible ligands and unambiguous structural determination both in solution and in the solid state ( Figure 2 and Figure 3). [19] This chiral derivative had never been resolved and no attempt had been made to determine a possible enantiomeric purity. Furthermore, this complex is formally an ªextended dimerº of mononuclear cation [Fe(2) 3 ] 2 for which we have observed a high diastereoselectivity in asymmetric induction experiments with TRISPHAT anions.…”

Section: Resultsmentioning

confidence: 99%

“…. P enantiomer of 4 (from the X-ray structural analysis of Elliott, [19] Cambridge crystallographic database [SADMIT]).…”

Section: Resultsmentioning

confidence: 99%

Efficient Resolution of a Dinuclear Triple Helicate by Asymmetric Extraction/Precipitation with TRISPHAT Anions as Resolving Agents

Jodry

Lacour

2000

Chemistry A European J

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Tetradentate 1,2-bis[4-(4'-methyl-2,2'-bipyridyl)]ethane ligand (3) and Fe(NH4)2(SO4)2.6H2O combine in a 3:2 ratio to form the racemic helicate [Fe2L3]4+ (4), as reported by Elliott et al. We now show that the enantiomeric purity of 4 can be efficiently measured by 1H NMR by the use of the TRISPHAT (1) salt as a chiral shift reagent. Large differences in chemical shifts (deltadeltadelta of up to 0.3 ppm, 20% [D6]DMSO in CD3CN) are observed between the enantiomers of 4 upon addition of [nBu4N][delta-1]. The resolution of 4 by asymmetric extraction was attempted: addition of an organic solution of [cinchonidinium][delta-1] salt (2 equiv) to an aqueous solution of helicate 4-(SO4)2 led, after vigorous stirring, to the extraction of the homochiral diastereomer [P-4][delta-1]4 into the organic layer along with the precipitation of the heterochiral diastereomer [M-4][delta-1]4 at the interface (diastereomeric ratio>49:1 for both processes). An enantioenriched fraction of [P-4][SO4]2 remained in the aqueous layer. To obtain only two fractions of resolved helicate and develop this procedure into an efficient resolution protocol, four equivalents of [cinchonidinium][delta-1] salt were used as the resolving agent. Chemically and diastereomerically pure [P-4][delta-1]4 and [M-4][delta-1]4 helicate salts were then obtained in excellent yields.

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“…This would be analogous to that involving ligand (6) [43] and to established Cu I Cu II [44] and intimated Ru II Ru III [45] species. It would also be complementary to such wellestablished Fe II Fe III mixed valence species as Prussian Blue, Fe 3 O(OAc) 6 3 ] 4+ with peroxodisulphate was slow, occurring at a rate similar to that of dissociation of the complex.…”

Section: Oxidationmentioning

confidence: 79%

Solvation and reactivity of a helical binuclear iron(II) complex with a tetradentate Schiff-base ligand

Blundell

Burgess

Hubbard

2005

Transition Met Chem

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Reaction of 2-acetylpyridine, hydrazine, and an iron(II) salt gives a low-spin binuclear iron(II) complex, [Fe 2 (pmk) 3 ] 4+ , in which three tetradentate Schiff base ligands span the two metal centres to give a complex of helical geometry. We report solubilities of the iodide and perchlorate salts, in H 2 O, in aqueous MeOH, and in aqueous DMSO (perchlorate only), up to 60% by vol of organic cosolvent. Transfer chemical potentials for the complex cation from H 2 O into the respective mixed solvents have been derived from these solubilities, to give a picture of solvation of this complex in the media studied. Kinetics of base hydrolysis of [Fe 2 (pmk) 3 ] 4+ have been established, in H 2 O and in 40% MeOH, 20 and 40% i-PrOH, and 20 and 40% DMSO, at 298.2 K. The reactivity of [Fe 2 (pmk) 3 ] 4+ is discussed in relation to reactivities of a selection of iron(II)-diimine complexes, ranging from [Fe(bipy) 3 ] 2+ and [Fe(phen) 3 ] 2+ to ligand-encapsulated cage complexes.

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A triply-bridged dinuclear tris(bipyridine)iron(II) complex: synthesis and electrochemical and structural studies

Cited by 116 publications

References 0 publications

Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing

Selective Metal‐Cation Recognition by [2.2]Ferrocenophanes: The Cases of Zinc‐ and Lithium‐Sensing

Efficient Resolution of a Dinuclear Triple Helicate by Asymmetric Extraction/Precipitation with TRISPHAT Anions as Resolving Agents

Solvation and reactivity of a helical binuclear iron(II) complex with a tetradentate Schiff-base ligand

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