(Ferrocenylthienyl) phosphines: Synthesis, electrochemistry and their use in Suzuki-Miyaura C, C coupling

Christian Gaebler, J. Matthaeus Speck, Marcus Korb, Dieter Schaarschmidt, Heinrich Lang

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

(Ferrocenylthienyl)phosphines of type 2-PR2-5-Fc-(C4H2S)-C-c (R = Ph (3a), Bu-t (3b)) and 2-PR2-3,4-Fc(2)-(C4HS)-C-c (R = Ph (4a), Bu-t (4b); Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) and their selenium derivatives were synthesized by consecutive synthetic methodologies. The molecular structure of 3a and 4a, b in the solid state show inter-and intramolecular (T-shaped) pep interactions for 3a and 4a, resulting in dimeric and 1D polymeric structures.

Phosphines 3a, b and 4a, b were applied in the Pd-catalyzed Suzuki-Miyaura C,C cross coupling reaction of aryl halides and boronic acids yielding the respective biaryls. Compound 3b shows a higher activity in C, C cross coupling reactions as compared to 3a and previously published thiophene-based phosphines and aminophosphines. Moreover sterically hindered and deactivated aryl bromides could be coupled at Pd loadings as low as 0.05 mol-% and at temperatures between 25 degrees C and 50 degrees C. However, the application of diferrocenylthienylphosphines 4a, b in Suzuki-Miyaura reactions resulted in decreased yields of the corresponding biaryls.

In the context of electrochemical investigations on these compounds, a strong dependency of the individual electrode reactions on the phosphorus substituents were found. During UV-Vis/NIR spectroelectrochemical studies, only a very limited iron-iron electronic interaction in 4a-Se+ could be detected. Thus, 4a-Se+ corresponds to a very weak coupled class II system according to the classification of Robin and Day. (C) 2016 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)26-35
Number of pages10
JournalJournal of Organometallic Chemistry
Volume813
DOIs
Publication statusPublished - 1 Jul 2016
Externally publishedYes

Cite this

Gaebler, Christian ; Speck, J. Matthaeus ; Korb, Marcus ; Schaarschmidt, Dieter ; Lang, Heinrich. / (Ferrocenylthienyl) phosphines : Synthesis, electrochemistry and their use in Suzuki-Miyaura C, C coupling. In: Journal of Organometallic Chemistry. 2016 ; Vol. 813. pp. 26-35.
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(Ferrocenylthienyl) phosphines : Synthesis, electrochemistry and their use in Suzuki-Miyaura C, C coupling. / Gaebler, Christian; Speck, J. Matthaeus; Korb, Marcus; Schaarschmidt, Dieter; Lang, Heinrich.

In: Journal of Organometallic Chemistry, Vol. 813, 01.07.2016, p. 26-35.

Research output: Contribution to journalArticle

TY - JOUR

T1 - (Ferrocenylthienyl) phosphines

T2 - Synthesis, electrochemistry and their use in Suzuki-Miyaura C, C coupling

AU - Gaebler, Christian

AU - Speck, J. Matthaeus

AU - Korb, Marcus

AU - Schaarschmidt, Dieter

AU - Lang, Heinrich

PY - 2016/7/1

Y1 - 2016/7/1

N2 - (Ferrocenylthienyl)phosphines of type 2-PR2-5-Fc-(C4H2S)-C-c (R = Ph (3a), Bu-t (3b)) and 2-PR2-3,4-Fc(2)-(C4HS)-C-c (R = Ph (4a), Bu-t (4b); Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) and their selenium derivatives were synthesized by consecutive synthetic methodologies. The molecular structure of 3a and 4a, b in the solid state show inter-and intramolecular (T-shaped) pep interactions for 3a and 4a, resulting in dimeric and 1D polymeric structures.Phosphines 3a, b and 4a, b were applied in the Pd-catalyzed Suzuki-Miyaura C,C cross coupling reaction of aryl halides and boronic acids yielding the respective biaryls. Compound 3b shows a higher activity in C, C cross coupling reactions as compared to 3a and previously published thiophene-based phosphines and aminophosphines. Moreover sterically hindered and deactivated aryl bromides could be coupled at Pd loadings as low as 0.05 mol-% and at temperatures between 25 degrees C and 50 degrees C. However, the application of diferrocenylthienylphosphines 4a, b in Suzuki-Miyaura reactions resulted in decreased yields of the corresponding biaryls.In the context of electrochemical investigations on these compounds, a strong dependency of the individual electrode reactions on the phosphorus substituents were found. During UV-Vis/NIR spectroelectrochemical studies, only a very limited iron-iron electronic interaction in 4a-Se+ could be detected. Thus, 4a-Se+ corresponds to a very weak coupled class II system according to the classification of Robin and Day. (C) 2016 Elsevier B.V. All rights reserved.

AB - (Ferrocenylthienyl)phosphines of type 2-PR2-5-Fc-(C4H2S)-C-c (R = Ph (3a), Bu-t (3b)) and 2-PR2-3,4-Fc(2)-(C4HS)-C-c (R = Ph (4a), Bu-t (4b); Fc = Fe(eta(5)-C5H4)(eta(5)-C5H5)) and their selenium derivatives were synthesized by consecutive synthetic methodologies. The molecular structure of 3a and 4a, b in the solid state show inter-and intramolecular (T-shaped) pep interactions for 3a and 4a, resulting in dimeric and 1D polymeric structures.Phosphines 3a, b and 4a, b were applied in the Pd-catalyzed Suzuki-Miyaura C,C cross coupling reaction of aryl halides and boronic acids yielding the respective biaryls. Compound 3b shows a higher activity in C, C cross coupling reactions as compared to 3a and previously published thiophene-based phosphines and aminophosphines. Moreover sterically hindered and deactivated aryl bromides could be coupled at Pd loadings as low as 0.05 mol-% and at temperatures between 25 degrees C and 50 degrees C. However, the application of diferrocenylthienylphosphines 4a, b in Suzuki-Miyaura reactions resulted in decreased yields of the corresponding biaryls.In the context of electrochemical investigations on these compounds, a strong dependency of the individual electrode reactions on the phosphorus substituents were found. During UV-Vis/NIR spectroelectrochemical studies, only a very limited iron-iron electronic interaction in 4a-Se+ could be detected. Thus, 4a-Se+ corresponds to a very weak coupled class II system according to the classification of Robin and Day. (C) 2016 Elsevier B.V. All rights reserved.

KW - Suzuki-Miyaura C,C cross-coupling

KW - Ferrocene

KW - Phosphine

KW - Solid state structure

KW - Electrochemistry

KW - NUCLEAR-MAGNETIC-RESONANCE

KW - MIXED-VALENCE COMPOUNDS

KW - CYCLIC VOLTAMMETRY

KW - ELECTRON-TRANSFER

KW - REDOX PROPERTIES

KW - HETEROARYLPHOSPHORUS COMPOUNDS

KW - ORGANOPHOSPHORUS COMPOUNDS

KW - 5-MEMBERED HETEROCYCLES

KW - DELTA-E-1/2 VALUES

KW - FERROCENE LIGANDS

U2 - 10.1016/j.jorganchem.2016.03.027

DO - 10.1016/j.jorganchem.2016.03.027

M3 - Article

VL - 813

SP - 26

EP - 35

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -