A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

Xiuxiu Yang; Thomas L. Gianetti; Michael D. Wörle; Nicolaas P. Van Leest; Bas De Bruin; Hansjörg Grützmacher

doi:10.1039/c8sc02864h

A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

Xiuxiu Yang, Thomas L. Gianetti, Michael D. Wörle, Nicolaas P. Van Leest, Bas De Bruin, Hansjörg Grützmacher

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

The dinuclear ruthenium complex [Ru₂H(μ-H)(Me₂dad)(dbcot)₂] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me₂dad) as a non-innocent bridging ligand between the metal centers to give a [Ru₂(Me₂dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H₂ to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K₂ and K₃ to their corresponding hydroquinone equivalents without affecting the CC double bonds. Mechanistic studies suggest that the [Ru₂(Me₂dad)] moiety, like hydrogenases, reacts with H₂ and releases electrons and protons stepwise.

Original language	English (US)
Pages (from-to)	1117-1125
Number of pages	9
Journal	Chemical Science
Volume	10
Issue number	4
DOIs	https://doi.org/10.1039/c8sc02864h
State	Published - 2019

ASJC Scopus subject areas

Chemistry(all)

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10.1039/c8sc02864h

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@article{9dc2744531724d2dbcb93a600f0e48b5,

title = "A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones",

abstract = "The dinuclear ruthenium complex [Ru2H(μ-H)(Me2dad)(dbcot)2] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me2dad) as a non-innocent bridging ligand between the metal centers to give a [Ru2(Me2dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K2 and K3 to their corresponding hydroquinone equivalents without affecting the CC double bonds. Mechanistic studies suggest that the [Ru2(Me2dad)] moiety, like hydrogenases, reacts with H2 and releases electrons and protons stepwise.",

author = "Xiuxiu Yang and Gianetti, {Thomas L.} and W{\"o}rle, {Michael D.} and {Van Leest}, {Nicolaas P.} and {De Bruin}, Bas and Hansj{\"o}rg Gr{\"u}tzmacher",

note = "Funding Information: We thank Dr Reinhard O. Kissner and Jean-Pierre H. Oudsen for their kind help with EPR measurements. This work was supported by the Swiss National Science Foundation and the ETH Z{\"u}rich. X. Y. is grateful for nancial support from the China Scholarship Council. T. L. G. was supported by the ETH Z{\"u}rich Postdoctoral Fellowship Program, co-funded by the ETH Zurich-Marie Curie action for people (FEL-14 15-1). Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c8sc02864h",

language = "English (US)",

volume = "10",

pages = "1117--1125",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "4",

}

TY - JOUR

T1 - A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

AU - Yang, Xiuxiu

AU - Gianetti, Thomas L.

AU - Wörle, Michael D.

AU - Van Leest, Nicolaas P.

AU - De Bruin, Bas

AU - Grützmacher, Hansjörg

N1 - Funding Information: We thank Dr Reinhard O. Kissner and Jean-Pierre H. Oudsen for their kind help with EPR measurements. This work was supported by the Swiss National Science Foundation and the ETH Zürich. X. Y. is grateful for nancial support from the China Scholarship Council. T. L. G. was supported by the ETH Zürich Postdoctoral Fellowship Program, co-funded by the ETH Zurich-Marie Curie action for people (FEL-14 15-1). Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - The dinuclear ruthenium complex [Ru2H(μ-H)(Me2dad)(dbcot)2] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me2dad) as a non-innocent bridging ligand between the metal centers to give a [Ru2(Me2dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K2 and K3 to their corresponding hydroquinone equivalents without affecting the CC double bonds. Mechanistic studies suggest that the [Ru2(Me2dad)] moiety, like hydrogenases, reacts with H2 and releases electrons and protons stepwise.

AB - The dinuclear ruthenium complex [Ru2H(μ-H)(Me2dad)(dbcot)2] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me2dad) as a non-innocent bridging ligand between the metal centers to give a [Ru2(Me2dad)] core. In addition, each ruthenium is bound to one dibenzo[a,e]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K2 and K3 to their corresponding hydroquinone equivalents without affecting the CC double bonds. Mechanistic studies suggest that the [Ru2(Me2dad)] moiety, like hydrogenases, reacts with H2 and releases electrons and protons stepwise.

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U2 - 10.1039/c8sc02864h

DO - 10.1039/c8sc02864h

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SN - 2041-6520

VL - 10

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EP - 1125

JO - Chemical Science

JF - Chemical Science

IS - 4

ER -

A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

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CCDC 1535559: Experimental Crystal Structure Determination

CCDC 1535510: Experimental Crystal Structure Determination

CCDC 1535543: Experimental Crystal Structure Determination

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A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones

Abstract

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Datasets

CCDC 1535559: Experimental Crystal Structure Determination

CCDC 1535510: Experimental Crystal Structure Determination

CCDC 1535543: Experimental Crystal Structure Determination

Cite this