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Three-way cooperativity in d8 metal complexes with ligands displaying chemical and redox non-innocence.

Reversible proton- and electron-transfer steps are crucial for various chemical transformations. The electron-reservoir behavior of redox non-innocent ligands and the proton-reservoir behavior of chemically non-innocent ligands can be cooperatively utilized for substrate bond activation. Although si... Full description

Journal Title: Chemistry (Weinheim an der Bergstrasse Germany), November 10, 2014, Vol.20(46), pp.15178-15187
Main Author: Deibel, Naina
Other Authors: Hohloch, Stephan , Schweinfurth, David , Weisser, Fritz , Grupp, Anita , Sarkar, Biprajit
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201403276
Link: http://search.proquest.com/docview/1619315898/?pq-origsite=primo
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title: Three-way cooperativity in d8 metal complexes with ligands displaying chemical and redox non-innocence.
format: Article
creator:
  • Deibel, Naina
  • Hohloch, Stephan
  • Schweinfurth, David
  • Weisser, Fritz
  • Grupp, Anita
  • Sarkar, Biprajit
subjects:
  • Alkadienes–Chemistry
  • Benzoquinones–Chemistry
  • Coordination Complexes–Chemistry
  • Electron Transport–Chemistry
  • Electrons–Chemistry
  • Ligands–Chemistry
  • Models, Molecular–Chemistry
  • Oxidation-Reduction–Chemistry
  • Protons–Chemistry
  • Alkadienes
  • Benzoquinones
  • Coordination Complexes
  • Ligands
  • Protons
  • 1,5-Cyclooctadiene
  • Quinone
  • Bond Activation
  • Electron Transfer
  • Ligand Effects
  • Quinones
ispartof: Chemistry (Weinheim an der Bergstrasse, Germany), November 10, 2014, Vol.20(46), pp.15178-15187
description: Reversible proton- and electron-transfer steps are crucial for various chemical transformations. The electron-reservoir behavior of redox non-innocent ligands and the proton-reservoir behavior of chemically non-innocent ligands can be cooperatively utilized for substrate bond activation. Although site-decoupled proton- and electron-transfer steps are often found in enzymatic systems, generating model metal complexes with these properties remains challenging. To tackle this issue, we present herein complexes [(cod sub(-H))M( mu -L super(2-))M(cod sub(-H))] (M=Pt super(II), [1] or Pd super(II), [2], cod=1,5-cyclooctadiene, H sub(2)L=2,5-di-[2,6-(diisopropyl)anilino]-1,4-be nzoquinone), in which cod acts as a proton reservoir, and L super(2-) as an electron reservoir. Protonation of [2] leads to an unusual tetranuclear complex. However, [1] can be stepwise reversibly protonated with up to two protons on the cod sub(-H) ligands, and the protonated forms can be stepwise reversibly reduced with up to two electrons on the L super(2-) ligand. The doubly protonated form of [1] is also shown to react with OMe super(-) leading to an activation of the cod ligands. The site-decoupled proton and electron reservoir sources work in tandem in a three-way cooperative process that results in the transfer of two electrons and two protons to a substrate leading to its double reduction and protonation. These results will possibly provide new insights into developing catalysts for multiple proton- and electron-transfer reactions by using metal complexes of non-innocent ligands. Spectroelectrochemistry: Site-decoupled proton- and electron-transfer steps have been characterized by using an arsenal of crystallographic, spectroscopic, and spectroelectrochemical methods. The protons and electrons were shown to participate in cooperative bond-activation reactions (see scheme; Dipp=diisopropylphenyl).
language: eng
source:
identifier: E-ISSN: 1521-3765 ; DOI: 10.1002/chem.201403276
fulltext: fulltext
issn:
  • 15213765
  • 1521-3765
url: Link


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titleThree-way cooperativity in d8 metal complexes with ligands displaying chemical and redox non-innocence.
creatorDeibel, Naina ; Hohloch, Stephan ; Schweinfurth, David ; Weisser, Fritz ; Grupp, Anita ; Sarkar, Biprajit
contributorDeibel, Naina (correspondence author) ; Deibel, Naina (record owner)
ispartofChemistry (Weinheim an der Bergstrasse, Germany), November 10, 2014, Vol.20(46), pp.15178-15187
identifierE-ISSN: 1521-3765 ; DOI: 10.1002/chem.201403276
subjectAlkadienes–Chemistry ; Benzoquinones–Chemistry ; Coordination Complexes–Chemistry ; Electron Transport–Chemistry ; Electrons–Chemistry ; Ligands–Chemistry ; Models, Molecular–Chemistry ; Oxidation-Reduction–Chemistry ; Protons–Chemistry ; Alkadienes ; Benzoquinones ; Coordination Complexes ; Ligands ; Protons ; 1,5-Cyclooctadiene ; Quinone ; Bond Activation ; Electron Transfer ; Ligand Effects ; Quinones
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descriptionReversible proton- and electron-transfer steps are crucial for various chemical transformations. The electron-reservoir behavior of redox non-innocent ligands and the proton-reservoir behavior of chemically non-innocent ligands can be cooperatively utilized for substrate bond activation. Although site-decoupled proton- and electron-transfer steps are often found in enzymatic systems, generating model metal complexes with these properties remains challenging. To tackle this issue, we present herein complexes [(cod sub(-H))M( mu -L super(2-))M(cod sub(-H))] (M=Pt super(II), [1] or Pd super(II), [2], cod=1,5-cyclooctadiene, H sub(2)L=2,5-di-[2,6-(diisopropyl)anilino]-1,4-be nzoquinone), in which cod acts as a proton reservoir, and L super(2-) as an electron reservoir. Protonation of [2] leads to an unusual tetranuclear complex. However, [1] can be stepwise reversibly protonated with up to two protons on the cod sub(-H) ligands, and the protonated forms can be stepwise reversibly reduced with up to two electrons on the L super(2-) ligand. The doubly protonated form of [1] is also shown to react with OMe super(-) leading to an activation of the cod ligands. The site-decoupled proton and electron reservoir sources work in tandem in a three-way cooperative process that results in the transfer of two electrons and two protons to a substrate leading to its double reduction and protonation. These results will possibly provide new insights into developing catalysts for multiple proton- and electron-transfer reactions by using metal complexes of non-innocent ligands. Spectroelectrochemistry: Site-decoupled proton- and electron-transfer steps have been characterized by using an arsenal of crystallographic, spectroscopic, and spectroelectrochemical methods. The protons and electrons were shown to participate in cooperative bond-activation reactions (see scheme; Dipp=diisopropylphenyl).
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titleThree-way cooperativity in d8 metal complexes with ligands displaying chemical and redox non-innocence.
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