Direct arylation of ferrocenylacetylenes and ferrocenylethenes under autocatalytic Meerwein conditions

Nock, Heinrich; Schottenberger, Herwig

doi:10.1021/jo00077a024

Cited by 24 publications

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“…A common electrochemical feature of the complexes is the low E 1/2 of their Fc + /Fc‐couples in comparison with the reported E 1/2 of ethynylferrocene (Fc + −C≡CH/Fc−C≡CH = +254 mV vs. Cp 2 Fe + /Cp 2 Fe) 14. In other words, the Fc groups in the three dinuclear complexes are more reducing or electron‐rich than the one in the uncomplexed Fc−C≡C−H.…”

Section: Resultsmentioning

confidence: 82%

Electronic Interactions in Dinuclear Platinum and Palladium Ethynylferrocene and Ferrocenylvinylidene Complexes

Yip

Wong

et al. 2004

Eur J Inorg Chem

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The complex [Pd2(dppm)2(μ‐η1:η1‐H−C=C−Fc)Cl2] (2) and its vinylidene isomer [Pd2(dppm)2(μ‐C=CH−Fc)Cl2] (3) [dppm = bis(diphenylphosphanyl)methane, Fc = ferrocenyl unit, CpFeC5H4] have been synthesized and characterized by single‐crystal X‐ray diffraction. Both 2 and 3 are A‐frame structures with long Pd−Pd distances of 3.2055(9) Å (2) and 3.1002(2) Å (3), respectively, and square‐planar metal coordination. The cyclic voltammograms (CV) of the complexes are measured and compared with that of [Pt2(dppm)2(μ‐η1:η1‐H−C=C−Fc)Cl2] (1). The CV of 2 and 3 consist of a nearly reversible Fc‐oxidation, an irreversible oxidation and a small reversible couple. The E1/2 values (vs. Cp2Fe+/Cp2Fe) of the Fc‐groups in complexes 1−3 follow the order 2 (−75±8 mV) > 1 (−108±10 mV) > 3 (−124±8 mV). The difference in the E1/2 values is explained by the orbital interactions between the acetylene and vinylidene groups with Pt2 and Pd2 cores. Our analysis shows that the metal‐to‐ligand π back‐bonding and ligand‐to‐metal σ‐donation have determining effects on the electronic interactions between the dimetallic centers and the bridgehead ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Resultsmentioning

confidence: 82%

Electronic Interactions in Dinuclear Platinum and Palladium Ethynylferrocene and Ferrocenylvinylidene Complexes

Yip

Wong

et al. 2004

Eur J Inorg Chem

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“…The one‐electron oxidation of ethynylferrocene, 1 , is known to be chemically reversible on the CV time scale . On a longer time scale, however, it had been previously reported that the lifetime of 1 + is much less than that generally observed for non‐H‐terminated ethynylferrocenes, and it was postulated that 1 + quickly dimerizes with loss of H‐atoms to form the butadiyne compound Fc−C 4 −Fc (Fc=ferrocenyl) .…”

Section: Resultsmentioning

confidence: 99%

“…The one-electron oxidation of ethynylferrocene, 1, is known to be chemically reversible on the CV time scale. [9][10][11][12][13] On a longer time scale, however, it had been previously reported that the lifetime of 1 + is much less than that generally observed for non-H-terminated ethynylferrocenes, and it was postulated that 1 + quickly dimerizes with loss of H-atoms to form the butadiyne compound FcÀ C 4 À Fc (Fc = ferrocenyl). [10] In our hands, although we were not able isolate pure salts of 1 + , bulk anodic electrolysis of 1 in either dichloromethane or THF containing 0.1 M [NBu 4 ][PF 6 ] showed that 1 + is stable (longlived) when generated this way.…”

Section: Ethynylferrocene and Phenylethynylferrocenes (1-3)mentioning

confidence: 99%

Anodic Oxidation of Ethynylferrocene Derivatives in Homogeneous Solution and Following Anodic Deposition onto Glassy Carbon Electrodes

et al. 2019

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Eight ferrocene derivatives linked by either an ether, amine, or phenylacetylene moiety to a terminal ethynyl group were covalently deposited on glassy carbon electrodes by anodic electrochemical methods. The lithio activation method, in which the terminal hydrogen of the ethynyl group is replaced by a lithium atom before anodic oxidation, was successfully employed in all cases. Direct oxidation of the inactivated ethynyl group also resulted in surface deposition. Surface coverages between 1×10−10 mol cm−2 and 14×10−10 mol cm−2 were achieved. Cyclic voltammetry scans of the modified electrodes in pure electrolytes differed depending on the size of the supporting electrolyte anion, as little as half the current being measured for a [B(C6F5)4]− vs. [PF6]− solution, suggesting differences in ion transport near the electrode surface. An ether‐linked ethynylferrocenium ion (5+) was isolated after electrolytic and chemical oxidation of 5 and characterized by X‐Ray crystallography as its [SbCl6]− salt.

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“…The preparation o f lithium ferrocenylacetylide and subsequent transm etallation finally has been reported as m ethod o f choice in the Pdcatalysed coupling to squaric acid derivatives such as 3-ferrocenyl-4-(ferrocenylethynylene)cyclobut-3-en-l,2-dio n e and 3,4-bis(ferrocenylethynylene)-cyclobut-3-en-l,2-dione [32], w hich represent an additional class o f ethyne bridged D /A -system s and contribute to the m ore classical donor-acceptor sys tem s as 4-(ferrocenylethynylene)nitrobenzene, 4-(ferrocenylethynylene)cyanobenzene and 4-(ferrocenylethynylene)acetylbenzene [22,23].…”

Section: Resultsmentioning

confidence: 99%

“…The intense color o f cer tain system s, however, causes transparency prob lem s and nonlinear optical investigation o f salts and m ixed-valency m etal complexes in solution is restricted to the H yper-Rayleigh Scattering tech nique (H SR), w hich is the only m ethod avail able for determ ining the ß values of such com pounds [21]. Consequently, acceptor substituted ferrocenylethynes like 4-(ferrocenylethynylene)-cyanobenzene [7a, 22], 4-(ferrocenylethynylene)-acetylbenzene [23], 4-(ferrocenylethynylene)nitrobenzene [22,23] [24] [32]…”

Section: E Thynylferrocene D Eriva Tivesmentioning

confidence: 99%

Asymmetrie Ethynes. Syntheses of Ethynylferrocene Paradigms

Polin

Schottenberger

Schwarzhans

1996

Zeitschrift Für Naturforschung B

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Synthetic methods to bifunctional ethynes have been examined. Direct ethynylation, the Stephens-Castro reaction, the Pd-catalysed Hagihara coupling, transmetalation reactions and nucleophilic additions have been evaluated in the preparation of substituted ferrocenylethynes with intended use of these materials in electrochemical and nonlinear optical investigations. Asymmetric ferrocenylethynes are promising candidates for applications in contemporary materials science. Synthetically, 1,4-bis(ferrocenylethynylene)benzene (1), 1,3,5-tris(ferrocenylethynylene) benzene (2), and 9 ,10-bis(ferrocenylethynylene)anthracene (3) are obtained in high yields, whereas 4-ferrocenylethynylene-2,3,5,6-tetrafluorostyrene (4) and potassium (ferrocenylethynylene) triphenyl borate (5) are accessible in only moderate yields. Further extension of this chemistry to additional heteronuclear bimetallic coordination compounds has been attempted, but without success due to severe difficulties in both preparation and characterization of these materials.

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Direct arylation of ferrocenylacetylenes and ferrocenylethenes under autocatalytic Meerwein conditions

Cited by 24 publications

References 0 publications

Electronic Interactions in Dinuclear Platinum and Palladium Ethynylferrocene and Ferrocenylvinylidene Complexes

Electronic Interactions in Dinuclear Platinum and Palladium Ethynylferrocene and Ferrocenylvinylidene Complexes

Anodic Oxidation of Ethynylferrocene Derivatives in Homogeneous Solution and Following Anodic Deposition onto Glassy Carbon Electrodes

Asymmetrie Ethynes. Syntheses of Ethynylferrocene Paradigms

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