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

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

11 Scopus citations

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
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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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 = "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",

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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

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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DO - 10.1039/c8sc02864h

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EP - 1125

JO - Chemical Science

JF - Chemical Science

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

Abstract

ASJC Scopus subject areas

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CCDC 1535543: Experimental Crystal Structure Determination

CCDC 1535561: Experimental Crystal Structure Determination

CCDC 1852336: 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

ASJC Scopus subject areas

Access to Document

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Datasets

CCDC 1535543: Experimental Crystal Structure Determination

CCDC 1535561: Experimental Crystal Structure Determination

CCDC 1852336: Experimental Crystal Structure Determination

Cite this