An anionic dinuclear ruthenium dihydrogen complex of relevance for alkyne gem-hydrogenation

T. Biberger; N. Nothling; M. Leutzsch; Christopher P. Gordon; C. Coperet; A. Furstner

doi:10.1002/anie.202201311

An anionic dinuclear ruthenium dihydrogen complex of relevance for alkyne gem-hydrogenation

T. Biberger
, N. Nothling
, M. Leutzsch
, Christopher P. Gordon
, C. Coperet
, A. Furstner

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

7 Citations (Scopus)

Abstract

During an investigation into the fate of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions with formation of Grubbs-type ruthenium catalysts, it was found that the reaction of [(IPr)(η⁶-cymene)RuCl₂] with H₂ under UV-irradiation affords an anionic dinuclear σ-dihydrogen complex, which is thermally surprisingly robust. Not only are anionic σ-complexes in general exceedingly rare, but the newly formed species seems to be the first example lacking any structural attributes able to counterbalance the negative charge and, in so doing, prevent oxidative insertion of the metal centers into the ligated H₂ from occurring.

Original language	English
Article number	e202201311
Number of pages	6
Journal	Angewandte Chemie (International Edition)
Volume	61
Issue number	24
DOIs	https://doi.org/10.1002/anie.202201311
Publication status	Published - 13 Jun 2022

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© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

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© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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title = "An anionic dinuclear ruthenium dihydrogen complex of relevance for alkyne gem-hydrogenation",

abstract = "During an investigation into the fate of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions with formation of Grubbs-type ruthenium catalysts, it was found that the reaction of [(IPr)(η6-cymene)RuCl2] with H2 under UV-irradiation affords an anionic dinuclear σ-dihydrogen complex, which is thermally surprisingly robust. Not only are anionic σ-complexes in general exceedingly rare, but the newly formed species seems to be the first example lacking any structural attributes able to counterbalance the negative charge and, in so doing, prevent oxidative insertion of the metal centers into the ligated H2 from occurring.",

author = "T. Biberger and N. Nothling and M. Leutzsch and Gordon, \{Christopher P.\} and C. Coperet and A. Furstner",

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doi = "10.1002/anie.202201311",

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T1 - An anionic dinuclear ruthenium dihydrogen complex of relevance for alkyne gem-hydrogenation

AU - Biberger, T.

AU - Nothling, N.

AU - Leutzsch, M.

AU - Gordon, Christopher P.

AU - Coperet, C.

AU - Furstner, A.

PY - 2022/6/13

Y1 - 2022/6/13

N2 - During an investigation into the fate of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions with formation of Grubbs-type ruthenium catalysts, it was found that the reaction of [(IPr)(η6-cymene)RuCl2] with H2 under UV-irradiation affords an anionic dinuclear σ-dihydrogen complex, which is thermally surprisingly robust. Not only are anionic σ-complexes in general exceedingly rare, but the newly formed species seems to be the first example lacking any structural attributes able to counterbalance the negative charge and, in so doing, prevent oxidative insertion of the metal centers into the ligated H2 from occurring.

AB - During an investigation into the fate of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions with formation of Grubbs-type ruthenium catalysts, it was found that the reaction of [(IPr)(η6-cymene)RuCl2] with H2 under UV-irradiation affords an anionic dinuclear σ-dihydrogen complex, which is thermally surprisingly robust. Not only are anionic σ-complexes in general exceedingly rare, but the newly formed species seems to be the first example lacking any structural attributes able to counterbalance the negative charge and, in so doing, prevent oxidative insertion of the metal centers into the ligated H2 from occurring.

UR - https://hdl.handle.net/1959.7/uws:78369

U2 - 10.1002/anie.202201311

DO - 10.1002/anie.202201311

M3 - Article

SN - 1433-7851

VL - 61

JO - Angewandte Chemie (International Edition)

JF - Angewandte Chemie (International Edition)

IS - 24

M1 - e202201311

ER -

An anionic dinuclear ruthenium dihydrogen complex of relevance for alkyne gem-hydrogenation

Abstract

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