Coordination chemistry of perhalogenated cyclopentadienes and alkynes. XXVIII new high-yield synthesis of monobromoferrocene and simplified procedure for the synthesis of pentabromoferrocene. Molecular structures of 1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene

Sünkel, Karlheinz; Bernhartzeder, Stefanie

doi:10.1016/j.jorganchem.2010.12.028

Cited by 27 publications

(32 citation statements)

References 19 publications

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“…Classic H ... Br − and Br ... Br − bonds were found in the bromide 9. Similar Br ... Br − interactions have been observed in the structures of 2-bromoimidazolium bromides [16,18,[29][30][31], a related Br ... F contact in a 2-bromoimidazolium hexafluorophosphate [30], and a typical Br ... Br interaction for example in pentabromoferrocene [32]. Table 2.…”

Section: Resultssupporting

confidence: 62%

Halogen Interactions in 2,4,5-Tribromoimidazolium Salts

et al. 2012

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Section: Resultssupporting

confidence: 62%

Halogen Interactions in 2,4,5-Tribromoimidazolium Salts

et al. 2012

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“…15,16 After purification by column chromatography, complexes 1 -4 could be isolated as deep red to dark maroon solids and are very stable in the solid state as well as in solution toward moisture and air.…”

Section: Resultsmentioning

confidence: 99%

Metal–Metal Interaction in Fischer Carbene Complexes: A Study of Ferrocenyl and Biferrocenyl Tungsten Alkylidene Complexes

et al. 2013

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A series of ferrocenyl (Fc = ferrocenyl; fc = ferrocen-1,1'-diyl) and biferrocenyl (Bfc = 1',1''-biferrocenyl; bfc = 1',1''-biferrocen-1,1'''-diyl) mono-and biscarbene tungsten(0) complexes of the type [(CO) 5 W=C(OMe)R] (1, R = Fc; 3, R = Bfc) and [(CO) 5 W=C(OMe)-R'-(OMe)C=W(CO) 5 ] (2, R' = fc; 4, R' = bfc) were synthesized according to the classical synthetic methodology by reacting W(CO) 6 with LiR (R = Fc, fc, bfc), followed by a subsequent alkylation using methyl trifluoromethanesulfonate. Electrochemical investigations were carried out on these complexes to get a closer insight into the electronic properties of 1 -4. The ferrocenyl and biferrocenyl moieties in 1 -4 show reversible one electron redox events. It was further found that the Fischer carbene unit is reducible in an electrochemical one electron transfer process. For the tungsten carbonyl moieties, irreversible oxidation processes were found. In addition, charge transfer studies were performed on 1 -4 by the use of in situ UV-Vis-NIR and infrared spectroelectrochemical techniques. During the UV-Vis-NIR investigations typical low energy transitions for the mixed-valent biferrocenyl unit were found. A further observed high energy NIR absorption is attributed to a metal-metal charge transfer transition between the tungsten carbonyl fragment and the ferrocenyl/biferrocenyl group in the corresponding oxidized states, which can be described as class II systems according to Robin and Day. This assignment was verified by infrared spectroelectrochemical studies. The electrochemical investigations are supported by DFT calculations. The structural properties of 1 -4 in the solid state were investigated by single-crystal Xray diffraction studies showing no substituent effects on bond lengths and angles. The biferrocenyl derivatives exhibit synconformation of the ferrocenyl and carbene building blocks.

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“…This strategy allowed for controlled successive ortho-additions of bromine (Supporting Information, Figure S1). 47,48 Br 3 Fc was synthesized from Br 2 Fc with a high enough yield that a simple column and recrystallization resulted in pure Br 3 Fc. However, bromination of BrFc to make Br 2 Fc had a much lower yield, resulting in a 60:40 ratio of Br 2 Fc to BrFc.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

Hole Transfer from Photoexcited Quantum Dots: The Relationship between Driving Force and Rate

Olshansky

Ding

Lee³

et al. 2015

J. Am. Chem. Soc.

125

166

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We have investigated the relationship between driving force and rate for interfacial hole transfer from quantum dots (QDs). This relationship is experimentally explored by using six distinct molecular hole acceptors with an 800 meV range in driving force. Specifically, we have investigated ferrocene derivatives with alkyl thiol moieties that strongly bind to the surface of cadmium chalcogenide QDs. The redox potentials of these ligands are controlled by functionalization of the cyclopentadiene rings on ferrocene with electron withdrawing and donating substituents, thus providing an avenue for tuning the driving force for hole transfer while holding all other system parameters constant. The relative hole transfer rate constant from photoexcited CdSe/CdS core/shell QDs to tethered ferrocene derivatives is determined by measuring the photoluminescence quantum yield of these QD–molecular conjugates at varying ferrocene coverage, as determined via quantitative NMR. The resulting relationship between rate and energetic driving force for hole transfer is not well modeled by the standard two-state Marcus model, since no inverted region is observed. Alternative mechanisms for charge transfer are posited, including an Auger-assisted mechanism that provides a successful fit to the results. The observed relationship can be used to design QD–molecular systems that maximize interfacial charge transfer rates while minimizing energetic losses associated with the driving force.

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Coordination chemistry of perhalogenated cyclopentadienes and alkynes. XXVIII new high-yield synthesis of monobromoferrocene and simplified procedure for the synthesis of pentabromoferrocene. Molecular structures of 1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene

Cited by 27 publications

References 19 publications

Halogen Interactions in 2,4,5-Tribromoimidazolium Salts

Halogen Interactions in 2,4,5-Tribromoimidazolium Salts

Metal–Metal Interaction in Fischer Carbene Complexes: A Study of Ferrocenyl and Biferrocenyl Tungsten Alkylidene Complexes

Hole Transfer from Photoexcited Quantum Dots: The Relationship between Driving Force and Rate

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