Electronic interactions in gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole

Dominique Miesel, Alexander Hildebrandt, Marcus Korb, Heinrich Lang

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The synthesis of gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) is presented. Chloro(2,5-diferrocenyl-1-phenyl-1H-phosphole) gold (3) has successfully been prepared by the reaction of 1 with AuCl(SMe2) (2). Treatment of 2 with arylethyne (aryl = ferrocenyl, phenyl) using catalytical amounts of [CuI] and 1 equiv. of 1 gave arylethynyl-(2,5-diferrocenyl-1-phenyl-1H-phosphole)gold 4a and 4b (aryl: a = ferrocenyl; b = phenyl). Compound [mu-(1,4-phenylenedi-2,1-ethynediyl)]bis(2,5-diferrocenyl-1-phenyl-1H-phosphole)digold (5) could be synthesized by a similar procedure using 0.5 equiv. of 1,4-diethynylbenzene. The electrochemical properties of 3, 4a, b and 5 were investigated by cyclic and square wave voltammetry. In 3, 4a and 4b each ferrocenyl unit shows one reversible redox event with redox separations of the ferrocenyl moieties in 2,5 position of approximately 260 mV. In 5 two redox events for the four ferrocenyl groups were observed. Spectroelectrochemical measurements of 3, 4a and 4b reveal IVCT absorptions with intensities of 1100-1300 L mol(-1) cm(-1) and a full-width-at-half-height of approximate to 3650 cm(-1). In 5 two mixed-valent units are present per molecule and therefore, the intensity of the IVCT band is increased to 2700 L mol(-1) cm(-1). Compounds 3, 4a, b and 5 can be classified as moderately coupled class II systems according to Robin and Day. The complexation of the gold(I) fragment by the phosphorus atom leads to a decreased metal-metal interaction when compared to 1. (C) 2015 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)104-110
Number of pages7
JournalJournal of Organometallic Chemistry
Volume803
DOIs
Publication statusPublished - 1 Feb 2016
Externally publishedYes

Cite this

Miesel, Dominique ; Hildebrandt, Alexander ; Korb, Marcus ; Lang, Heinrich. / Electronic interactions in gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole. In: Journal of Organometallic Chemistry. 2016 ; Vol. 803. pp. 104-110.
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abstract = "The synthesis of gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) is presented. Chloro(2,5-diferrocenyl-1-phenyl-1H-phosphole) gold (3) has successfully been prepared by the reaction of 1 with AuCl(SMe2) (2). Treatment of 2 with arylethyne (aryl = ferrocenyl, phenyl) using catalytical amounts of [CuI] and 1 equiv. of 1 gave arylethynyl-(2,5-diferrocenyl-1-phenyl-1H-phosphole)gold 4a and 4b (aryl: a = ferrocenyl; b = phenyl). Compound [mu-(1,4-phenylenedi-2,1-ethynediyl)]bis(2,5-diferrocenyl-1-phenyl-1H-phosphole)digold (5) could be synthesized by a similar procedure using 0.5 equiv. of 1,4-diethynylbenzene. The electrochemical properties of 3, 4a, b and 5 were investigated by cyclic and square wave voltammetry. In 3, 4a and 4b each ferrocenyl unit shows one reversible redox event with redox separations of the ferrocenyl moieties in 2,5 position of approximately 260 mV. In 5 two redox events for the four ferrocenyl groups were observed. Spectroelectrochemical measurements of 3, 4a and 4b reveal IVCT absorptions with intensities of 1100-1300 L mol(-1) cm(-1) and a full-width-at-half-height of approximate to 3650 cm(-1). In 5 two mixed-valent units are present per molecule and therefore, the intensity of the IVCT band is increased to 2700 L mol(-1) cm(-1). Compounds 3, 4a, b and 5 can be classified as moderately coupled class II systems according to Robin and Day. The complexation of the gold(I) fragment by the phosphorus atom leads to a decreased metal-metal interaction when compared to 1. (C) 2015 Elsevier B.V. All rights reserved.",
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Electronic interactions in gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole. / Miesel, Dominique; Hildebrandt, Alexander; Korb, Marcus; Lang, Heinrich.

In: Journal of Organometallic Chemistry, Vol. 803, 01.02.2016, p. 104-110.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electronic interactions in gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole

AU - Miesel, Dominique

AU - Hildebrandt, Alexander

AU - Korb, Marcus

AU - Lang, Heinrich

PY - 2016/2/1

Y1 - 2016/2/1

N2 - The synthesis of gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) is presented. Chloro(2,5-diferrocenyl-1-phenyl-1H-phosphole) gold (3) has successfully been prepared by the reaction of 1 with AuCl(SMe2) (2). Treatment of 2 with arylethyne (aryl = ferrocenyl, phenyl) using catalytical amounts of [CuI] and 1 equiv. of 1 gave arylethynyl-(2,5-diferrocenyl-1-phenyl-1H-phosphole)gold 4a and 4b (aryl: a = ferrocenyl; b = phenyl). Compound [mu-(1,4-phenylenedi-2,1-ethynediyl)]bis(2,5-diferrocenyl-1-phenyl-1H-phosphole)digold (5) could be synthesized by a similar procedure using 0.5 equiv. of 1,4-diethynylbenzene. The electrochemical properties of 3, 4a, b and 5 were investigated by cyclic and square wave voltammetry. In 3, 4a and 4b each ferrocenyl unit shows one reversible redox event with redox separations of the ferrocenyl moieties in 2,5 position of approximately 260 mV. In 5 two redox events for the four ferrocenyl groups were observed. Spectroelectrochemical measurements of 3, 4a and 4b reveal IVCT absorptions with intensities of 1100-1300 L mol(-1) cm(-1) and a full-width-at-half-height of approximate to 3650 cm(-1). In 5 two mixed-valent units are present per molecule and therefore, the intensity of the IVCT band is increased to 2700 L mol(-1) cm(-1). Compounds 3, 4a, b and 5 can be classified as moderately coupled class II systems according to Robin and Day. The complexation of the gold(I) fragment by the phosphorus atom leads to a decreased metal-metal interaction when compared to 1. (C) 2015 Elsevier B.V. All rights reserved.

AB - The synthesis of gold(I) complexes of 2,5-diferrocenyl-1-phenyl-1H-phosphole (1) is presented. Chloro(2,5-diferrocenyl-1-phenyl-1H-phosphole) gold (3) has successfully been prepared by the reaction of 1 with AuCl(SMe2) (2). Treatment of 2 with arylethyne (aryl = ferrocenyl, phenyl) using catalytical amounts of [CuI] and 1 equiv. of 1 gave arylethynyl-(2,5-diferrocenyl-1-phenyl-1H-phosphole)gold 4a and 4b (aryl: a = ferrocenyl; b = phenyl). Compound [mu-(1,4-phenylenedi-2,1-ethynediyl)]bis(2,5-diferrocenyl-1-phenyl-1H-phosphole)digold (5) could be synthesized by a similar procedure using 0.5 equiv. of 1,4-diethynylbenzene. The electrochemical properties of 3, 4a, b and 5 were investigated by cyclic and square wave voltammetry. In 3, 4a and 4b each ferrocenyl unit shows one reversible redox event with redox separations of the ferrocenyl moieties in 2,5 position of approximately 260 mV. In 5 two redox events for the four ferrocenyl groups were observed. Spectroelectrochemical measurements of 3, 4a and 4b reveal IVCT absorptions with intensities of 1100-1300 L mol(-1) cm(-1) and a full-width-at-half-height of approximate to 3650 cm(-1). In 5 two mixed-valent units are present per molecule and therefore, the intensity of the IVCT band is increased to 2700 L mol(-1) cm(-1). Compounds 3, 4a, b and 5 can be classified as moderately coupled class II systems according to Robin and Day. The complexation of the gold(I) fragment by the phosphorus atom leads to a decreased metal-metal interaction when compared to 1. (C) 2015 Elsevier B.V. All rights reserved.

KW - Heterocycle

KW - Electrochemistry

KW - Electron transfer

KW - Phosphole

KW - UNSATURATED HYDROCARBON BRIDGES

KW - TRANSITION-METAL-COMPLEXES

KW - SOLID-STATE

KW - ALKYNYLGOLD(I) COMPLEXES

KW - ORGANOMETALLIC COMPLEXES

KW - 5-MEMBERED HETEROCYCLES

KW - CHARGE-TRANSFER

KW - BUILDING-BLOCK

KW - PHOSPHOLE

KW - ELECTROCHEMISTRY

U2 - 10.1016/j.jorganchem.2015.12.014

DO - 10.1016/j.jorganchem.2015.12.014

M3 - Article

VL - 803

SP - 104

EP - 110

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -