Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes

K.B. Vincent, Q. Zeng, M. Parthey, D.S. Yufit, J.A.K. Howard, F. Hartl, M. Kaupp, Paul Low

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Abstract

The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCH═C(C≡CR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV–vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCH═C(C≡CC6H4NH2-4)2]+ and [FcCH═C(C≡CC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCH═C(C≡CC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCH═C(C≡CC6H4NO2-4)2]2– could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.
Original languageEnglish
Pages (from-to)6022-6032
JournalOrganometallics
Volume32
Issue number20
Early online date9 Aug 2013
DOIs
Publication statusPublished - 28 Oct 2013

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Diynes
Molecular structure
Electronic structure
molecular structure
electronic structure
Derivatives
Alkynes
electrochemical oxidation
Electrochemical oxidation
cross coupling
alkynes
synthesis
aniline
entry
Passivation
passivity
Anions
Transistors
transistors
templates

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Vincent, K. B., Zeng, Q., Parthey, M., Yufit, D. S., Howard, J. A. K., Hartl, F., ... Low, P. (2013). Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes. Organometallics, 32(20), 6022-6032. https://doi.org/10.1021/om400535y
Vincent, K.B. ; Zeng, Q. ; Parthey, M. ; Yufit, D.S. ; Howard, J.A.K. ; Hartl, F. ; Kaupp, M. ; Low, Paul. / Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes. In: Organometallics. 2013 ; Vol. 32, No. 20. pp. 6022-6032.
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Vincent, KB, Zeng, Q, Parthey, M, Yufit, DS, Howard, JAK, Hartl, F, Kaupp, M & Low, P 2013, 'Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes' Organometallics, vol. 32, no. 20, pp. 6022-6032. https://doi.org/10.1021/om400535y

Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes. / Vincent, K.B.; Zeng, Q.; Parthey, M.; Yufit, D.S.; Howard, J.A.K.; Hartl, F.; Kaupp, M.; Low, Paul.

In: Organometallics, Vol. 32, No. 20, 28.10.2013, p. 6022-6032.

Research output: Contribution to journalArticle

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T1 - Syntheses, Spectroelectrochemical Studies, and Molecular and Electronic Structures of Ferrocenyl Ene-diynes

AU - Vincent, K.B.

AU - Zeng, Q.

AU - Parthey, M.

AU - Yufit, D.S.

AU - Howard, J.A.K.

AU - Hartl, F.

AU - Kaupp, M.

AU - Low, Paul

PY - 2013/10/28

Y1 - 2013/10/28

N2 - The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCH═C(C≡CR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV–vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCH═C(C≡CC6H4NH2-4)2]+ and [FcCH═C(C≡CC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCH═C(C≡CC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCH═C(C≡CC6H4NO2-4)2]2– could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.

AB - The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCH═C(C≡CR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV–vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCH═C(C≡CC6H4NH2-4)2]+ and [FcCH═C(C≡CC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCH═C(C≡CC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCH═C(C≡CC6H4NO2-4)2]2– could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.

U2 - 10.1021/om400535y

DO - 10.1021/om400535y

M3 - Article

VL - 32

SP - 6022

EP - 6032

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 20

ER -