Redox‐functionalized Ligands: From Molecular Electrochemical Sensors to Nanostructured Surfaces

Siemeling, Ulrich

doi:10.1002/zaac.200500270

Cited by 17 publications

(8 citation statements)

References 86 publications

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“…Ferrocene is an emblematic organometallic molecule, which exhibits high chemical and physical stability, unique rotational features, and exceptionally well‐defined redox capabilities [1,2] . These attributes have acted as inspiration for organometallic chemists, who have applied a wide‐range of synthetic techniques to tailor ferrocene‐containing molecules towards diverse applications in surface science, [3–10] sensing, [11–18] biochemistry, [19–27] catalysis, [28–34] and molecular electronics [35–49] …”

Section: Introductionmentioning

confidence: 99%

“…[1,2] These attributes have acted as inspiration for organometallic chemists, who have applied a wide-range of synthetic techniques to tailor ferrocene-containing molecules towards diverse applications in surface science, [3][4][5][6][7][8][9][10] sensing, [11][12][13][14][15][16][17][18] biochemistry, [19][20][21][22][23][24][25][26][27] catalysis, [28][29][30][31][32][33][34] and molecular electronics. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Further to this, ferrocene has garnered significant interest in the development of macrocyclic molecules. ...…”

Section: Introductionmentioning

confidence: 99%

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Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

2022

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Multiple synthetic pathways were explored for the preparation of ethynylarene-containing ferrocenylene macrocyles. Accordingly, the synthesis of novel bis-and tris-ferrocenylene macrocycles, containing a diethynylpyridine bridging group was achieved, and evidence is also provided for a number of linearanalogues formed as by-products. The electrochemical properties of the macrocycles were examined, and it was shown that the number of observable redox processes does not necessarily correlate with the number of redox active centres. Additionally, examination of the comproportionation constants of the trisferrocenylene macrocycle demonstrated that the monocationic and dicationic species could be assigned to class II and I/II borderline of the Robin-Day classification, respectively. The synthesis of these molecules presents an opportunity towards the development of conjugated ferrocenylene macrocycles for electronic applications.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

2022

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“…The study of transition-metal complexes based on redox noninnocent ligands has become the subject of widespread attention in recent years. − Several excellent reviews on this topic have appeared, detailing the various types of noninnocent ligands available and the mechanisms through which they influence the reactivity of a metal complex, with a particular emphasis on the field of catalysis. − However, the potential field of application of these systems is not restricted to catalysis, but includes other areas such as ion sensing and the synthesis of functional molecular materials. ,,− …”

Section: Introductionmentioning

confidence: 99%

Coinage Metal Complexes of Tris(pyrazolyl)methanide-Based Redox-Active Metalloligands

et al. 2014

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A series of coinage metal complexes containing the redox-active metalloligands [RuCp X (κ 3 N-Tpmd)] {κ 3 N-Tpmd = κ 3 N-[C(pz) 3 ] with pz = pyrazolyl; [RuCp(Tpmd)] (2a) and [RuCp*(Tpmd)] (2b)} are presented. 2a and 2b are isolable, relatively stable compounds, despite the fact that they feature a "naked" carbanion at the bridgehead position of the κ 3 N-coordinated tris(pyrazolyl)methanide ligand scaffold. As expected, both complexes act as κ 1 C ligands toward coinage metal fragments to yield dinuclear complexes of the general formulaAll complexes under study were fully characterized by common spectroscopic techniques; the structural parameters of 2a, 3a, 5a, 6a, 7a, and 10a were determined by X-ray diffraction. Coordination of the {MX} fragment leads to electronic effects on the metalloligand unit, as reflected by the corresponding 1 H and 13 C NMR spectra. Density functional theory calculations were performed in order to elucidate a conceivable interplay between the metal atoms. The bonding characteristics within the {MX} fragment are only marginally affected upon electronic excitation of the ruthenium-based metalloligand. However, some effect of the influence of {MX} on the E 0 1/2 (Ru II /Ru III ) value was detected with the aid of cyclic voltammetry measurements. A strong Lewis-acidic metal fragment such as GaCl 3 (11a) leads to an E 0 1/2 value of 0.37 V, while electron-richer coinage metal fragments facilitate the oxidation of the ruthenium center significantly (E 0 1/2 = 0.14−0.23 V). This dependence suggests an interaction between both metals due to their close spatial proximity.

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“…We have previously reported the ring opening of 1-methylimidazole (Scheme ) ,, mediated by scandium and yttrium alkyl complexes supported by a ferrocene-diamide ligand, (NN fc )M(CH 2 Ar)(THF) ( 1 M -THF : NN fc = fc(NSi t BuMe 2 ) 2 , fc =1,1′-ferrocenylene; M = Sc, Ar = 3,5-Me 2 C 6 H 3 ; M = Y, Ar = C 6 H 5 ). − Those examples added to the series of homogeneous systems that mediate the ring opening of N-heterocycles and involve tantalum, − , niobium, − titanium, , rhenium, , and uranium complexes …”

Section: Introductionmentioning

confidence: 99%

Reactions of Imidazoles with Electrophilic Metal Alkyl Complexes

et al. 2010

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The C−C coupling of two molecules of 1-methylbenzimidazole was effected by neutral yttrium and lutetium benzyl complexes supported by a 1,1′-ferrocenylene-diamide ligand. This transformation involves the C−H activation and coupling of one η2(N,C)-imidazolyl fragment with a coordinated 1-methylbenzimidazole ligand. The coupled product can be transformed into a mono- or dinuclear product, in which one of the imidazole rings is cleaved. Variable-temperature 1H and 2H NMR spectroscopic data support the reversibility of the C−C coupling event and explain the formation of the dinuclear product.

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Redox‐functionalized Ligands: From Molecular Electrochemical Sensors to Nanostructured Surfaces

Cited by 17 publications

References 86 publications

Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

Development and Characterisation of Highly Conjugated Functionalised Ferrocenylene Macrocycles

Coinage Metal Complexes of Tris(pyrazolyl)methanide-Based Redox-Active Metalloligands

Reactions of Imidazoles with Electrophilic Metal Alkyl Complexes

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