Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes

Ulrike Pfaff, Alexander Hildebrandt, Marcus Korb, Steffen Osswald, Michael Linseis, Katja Schreiter, Stefan Spange, Rainer F. Winter, Heinrich Lang

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

Complexes [{Ru(CO)Cl(PiPr(3))(2)}(2)(mu-2,5-(CH=CH)(2)-(C4H2E)-C-c] (E=NR; R=C6H4-4-NMe2 (10a), C6H4-4-OMe (10b), C6H4-4-Me (10c), C6H5 (10d), C6H4-4-CO2Et (10e), C6H4-4-NO2 (10 f), C6H3-3,5-(CF3)(2) (10g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro) electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with Delta E degrees'=350-495 mV. A linear relationship between Delta E degrees' and the sigma(p) Hammett constant for 10a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+)-13(+) confirm full charge delocalization over the {Ru} CH=CH-heterocycle-CH=CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.

Original languageEnglish
Pages (from-to)783-801
Number of pages19
JournalCHEMISTRY-A EUROPEAN JOURNAL
Volume22
Issue number2
DOIs
Publication statusPublished - 11 Jan 2016
Externally publishedYes

Cite this

Pfaff, U., Hildebrandt, A., Korb, M., Osswald, S., Linseis, M., Schreiter, K., ... Lang, H. (2016). Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes. CHEMISTRY-A EUROPEAN JOURNAL, 22(2), 783-801. https://doi.org/10.1002/chem.201503687
Pfaff, Ulrike ; Hildebrandt, Alexander ; Korb, Marcus ; Osswald, Steffen ; Linseis, Michael ; Schreiter, Katja ; Spange, Stefan ; Winter, Rainer F. ; Lang, Heinrich. / Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes. In: CHEMISTRY-A EUROPEAN JOURNAL. 2016 ; Vol. 22, No. 2. pp. 783-801.
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abstract = "Complexes [{Ru(CO)Cl(PiPr(3))(2)}(2)(mu-2,5-(CH=CH)(2)-(C4H2E)-C-c] (E=NR; R=C6H4-4-NMe2 (10a), C6H4-4-OMe (10b), C6H4-4-Me (10c), C6H5 (10d), C6H4-4-CO2Et (10e), C6H4-4-NO2 (10 f), C6H3-3,5-(CF3)(2) (10g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro) electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with Delta E degrees'=350-495 mV. A linear relationship between Delta E degrees' and the sigma(p) Hammett constant for 10a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+)-13(+) confirm full charge delocalization over the {Ru} CH=CH-heterocycle-CH=CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.",
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Pfaff, U, Hildebrandt, A, Korb, M, Osswald, S, Linseis, M, Schreiter, K, Spange, S, Winter, RF & Lang, H 2016, 'Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes' CHEMISTRY-A EUROPEAN JOURNAL, vol. 22, no. 2, pp. 783-801. https://doi.org/10.1002/chem.201503687

Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes. / Pfaff, Ulrike; Hildebrandt, Alexander; Korb, Marcus; Osswald, Steffen; Linseis, Michael; Schreiter, Katja; Spange, Stefan; Winter, Rainer F.; Lang, Heinrich.

In: CHEMISTRY-A EUROPEAN JOURNAL, Vol. 22, No. 2, 11.01.2016, p. 783-801.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes

AU - Pfaff, Ulrike

AU - Hildebrandt, Alexander

AU - Korb, Marcus

AU - Osswald, Steffen

AU - Linseis, Michael

AU - Schreiter, Katja

AU - Spange, Stefan

AU - Winter, Rainer F.

AU - Lang, Heinrich

PY - 2016/1/11

Y1 - 2016/1/11

N2 - Complexes [{Ru(CO)Cl(PiPr(3))(2)}(2)(mu-2,5-(CH=CH)(2)-(C4H2E)-C-c] (E=NR; R=C6H4-4-NMe2 (10a), C6H4-4-OMe (10b), C6H4-4-Me (10c), C6H5 (10d), C6H4-4-CO2Et (10e), C6H4-4-NO2 (10 f), C6H3-3,5-(CF3)(2) (10g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro) electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with Delta E degrees'=350-495 mV. A linear relationship between Delta E degrees' and the sigma(p) Hammett constant for 10a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+)-13(+) confirm full charge delocalization over the {Ru} CH=CH-heterocycle-CH=CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.

AB - Complexes [{Ru(CO)Cl(PiPr(3))(2)}(2)(mu-2,5-(CH=CH)(2)-(C4H2E)-C-c] (E=NR; R=C6H4-4-NMe2 (10a), C6H4-4-OMe (10b), C6H4-4-Me (10c), C6H5 (10d), C6H4-4-CO2Et (10e), C6H4-4-NO2 (10 f), C6H3-3,5-(CF3)(2) (10g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro) electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with Delta E degrees'=350-495 mV. A linear relationship between Delta E degrees' and the sigma(p) Hammett constant for 10a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+)-13(+) confirm full charge delocalization over the {Ru} CH=CH-heterocycle-CH=CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations.

KW - 5-membered heterocycles

KW - class III Robin and Day

KW - density functional calculations

KW - ruthenium

KW - spectroelectrochemistry

KW - VALENCE RUTHENIUM COMPLEXES

KW - AB-INITIO PSEUDOPOTENTIALS

KW - VINYL-RUTHENIUM

KW - 5-MEMBERED HETEROCYCLES

KW - TRIRUTHENIUM COMPLEXES

KW - NONAQUEOUS SOLVENTS

KW - ABSORPTION-SPECTRA

KW - POLARIZABILITY SP

KW - OSMIUM COMPLEXES

KW - REDOX COUPLE

U2 - 10.1002/chem.201503687

DO - 10.1002/chem.201503687

M3 - Article

VL - 22

SP - 783

EP - 801

JO - CHEMISTRY-A EUROPEAN JOURNAL

JF - CHEMISTRY-A EUROPEAN JOURNAL

SN - 0947-6539

IS - 2

ER -