Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes

Michael Rauch; Sayan Kar; Amit Kumar; Liat Avram; Linda J W Shimon; David Milstein

doi:10.1021/jacs.0c05500

Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes

Michael Rauch, Sayan Kar, Amit Kumar, Liat Avram, Linda J W Shimon, David Milstein

School of Chemistry

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

Abstract

A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones under relatively mild conditions is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facili-tating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

Original language	English
Pages (from-to)	14513-14521
Journal	Journal of the American Chemical Society
Volume	142
Issue number	34
Early online date	28 Jul 2020
DOIs	https://doi.org/10.1021/jacs.0c05500
Publication status	Published - 26 Aug 2020

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Rauch_2020_JACS_Metal-ligand_AAM
Copyright © 2020 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/jacs.0c05500
Accepted author manuscript, 1.87 MB

Amit Kumar
- ak336st-andrews.acuk
- School of Chemistry - Principal Research Fellow
Person: Academic - Research

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@article{bb8682bb1bae44fba3041ba595678d44,

title = "Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes",

abstract = "A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones under relatively mild conditions is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facili-tating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.",

author = "Michael Rauch and Sayan Kar and Amit Kumar and Liat Avram and Shimon, {Linda J W} and David Milstein",

note = "We thank the European Research Council (ERC AdG 692775) for support of this research. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship. S.K. acknowledges the Sustainability and Energy Research Initiative (SAERI) Weizmann Institute of Science for a research fellowship. A. K. is thankful to the Feinberg Graduate School for the Senior Postdoctoral Fellowship.",

year = "2020",

month = aug,

day = "26",

doi = "10.1021/jacs.0c05500",

language = "English",

volume = "142",

pages = "14513--14521",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society (ACS)",

number = "34",

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TY - JOUR

T1 - Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes

AU - Rauch, Michael

AU - Kar, Sayan

AU - Kumar, Amit

AU - Avram, Liat

AU - Shimon, Linda J W

AU - Milstein, David

N1 - We thank the European Research Council (ERC AdG 692775) for support of this research. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship. S.K. acknowledges the Sustainability and Energy Research Initiative (SAERI) Weizmann Institute of Science for a research fellowship. A. K. is thankful to the Feinberg Graduate School for the Senior Postdoctoral Fellowship.

PY - 2020/8/26

Y1 - 2020/8/26

N2 - A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones under relatively mild conditions is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facili-tating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

AB - A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones under relatively mild conditions is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facili-tating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

U2 - 10.1021/jacs.0c05500

DO - 10.1021/jacs.0c05500

M3 - Article

SN - 0002-7863

VL - 142

SP - 14513

EP - 14521

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

Metal-ligand cooperation facilitates bond activation and catalytic hydrogenation with zinc pincer complexes

Abstract

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