Synthesis of Ru-PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions

Hendrik A. Kempf; Germán López Robledo; Anke Spannenberg; Kathrin Junge; Haijun Jiao; Henrik Junge; Matthias Beller

doi:10.1002/cctc.202401481

Synthesis of Ru-PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions

Hendrik A. Kempf, Germán López Robledo, Anke Spannenberg, Kathrin Junge, Haijun Jiao, Henrik Junge, Matthias Beller

Leibniz-Institut für Katalyse

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

1 Scopus citations

Abstract

The reaction of N,N-bis(2-(diisopropylphosphaneyl)ethyl)prop-2-yn-1-amine 1 with [Ru(CO)ClH(PPh₃)₃] leads to the formation of a new class of cyclometallated PNPC pincer complexes. Several examples of this class of compounds are synthesized and characterized. They, specifically complexes 2 and 3, show good to excellent activity and selectivity in additive-free formic acid dehydrogenation, and transfer (de)hydrogenation reactions of different functional groups (ketone, alkyne, and alcohol). Theoretical and experimental studies reveal two competing pathways for the dehydrogenation of formic acid. The Ru-H pathway proceeds via the coordination site trans to the propylene arm of the ligand, whereas in the Ru-C pathway, a de-coordination of the propylene arm is observed.

Original language	English
Article number	e202401481
Journal	ChemCatChem
Volume	17
Issue number	3
DOIs	https://doi.org/10.1002/cctc.202401481
State	Published - 6 Feb 2025
Externally published	Yes

Keywords

Computational chemistry
Dehydrogenation
Homogeneous catalysis
Ruthenium-pincer complex
Transfer hydrogenation

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10.1002/cctc.202401481

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title = "Synthesis of Ru-PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions",

abstract = "The reaction of N,N-bis(2-(diisopropylphosphaneyl)ethyl)prop-2-yn-1-amine 1 with [Ru(CO)ClH(PPh3)3] leads to the formation of a new class of cyclometallated PNPC pincer complexes. Several examples of this class of compounds are synthesized and characterized. They, specifically complexes 2 and 3, show good to excellent activity and selectivity in additive-free formic acid dehydrogenation, and transfer (de)hydrogenation reactions of different functional groups (ketone, alkyne, and alcohol). Theoretical and experimental studies reveal two competing pathways for the dehydrogenation of formic acid. The Ru-H pathway proceeds via the coordination site trans to the propylene arm of the ligand, whereas in the Ru-C pathway, a de-coordination of the propylene arm is observed.",

keywords = "Computational chemistry, Dehydrogenation, Homogeneous catalysis, Ruthenium-pincer complex, Transfer hydrogenation",

author = "Kempf, {Hendrik A.} and {L{\'o}pez Robledo}, Germ{\'a}n and Anke Spannenberg and Kathrin Junge and Haijun Jiao and Henrik Junge and Matthias Beller",

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doi = "10.1002/cctc.202401481",

language = "English",

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T1 - Synthesis of Ru-PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions

AU - Kempf, Hendrik A.

AU - López Robledo, Germán

AU - Spannenberg, Anke

AU - Junge, Kathrin

AU - Jiao, Haijun

AU - Junge, Henrik

AU - Beller, Matthias

PY - 2025/2/6

Y1 - 2025/2/6

N2 - The reaction of N,N-bis(2-(diisopropylphosphaneyl)ethyl)prop-2-yn-1-amine 1 with [Ru(CO)ClH(PPh3)3] leads to the formation of a new class of cyclometallated PNPC pincer complexes. Several examples of this class of compounds are synthesized and characterized. They, specifically complexes 2 and 3, show good to excellent activity and selectivity in additive-free formic acid dehydrogenation, and transfer (de)hydrogenation reactions of different functional groups (ketone, alkyne, and alcohol). Theoretical and experimental studies reveal two competing pathways for the dehydrogenation of formic acid. The Ru-H pathway proceeds via the coordination site trans to the propylene arm of the ligand, whereas in the Ru-C pathway, a de-coordination of the propylene arm is observed.

AB - The reaction of N,N-bis(2-(diisopropylphosphaneyl)ethyl)prop-2-yn-1-amine 1 with [Ru(CO)ClH(PPh3)3] leads to the formation of a new class of cyclometallated PNPC pincer complexes. Several examples of this class of compounds are synthesized and characterized. They, specifically complexes 2 and 3, show good to excellent activity and selectivity in additive-free formic acid dehydrogenation, and transfer (de)hydrogenation reactions of different functional groups (ketone, alkyne, and alcohol). Theoretical and experimental studies reveal two competing pathways for the dehydrogenation of formic acid. The Ru-H pathway proceeds via the coordination site trans to the propylene arm of the ligand, whereas in the Ru-C pathway, a de-coordination of the propylene arm is observed.

KW - Computational chemistry

KW - Dehydrogenation

KW - Homogeneous catalysis

KW - Ruthenium-pincer complex

KW - Transfer hydrogenation

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U2 - 10.1002/cctc.202401481

DO - 10.1002/cctc.202401481

M3 - Article

AN - SCOPUS:85210118227

SN - 1867-3880

VL - 17

JO - ChemCatChem

JF - ChemCatChem

IS - 3

M1 - e202401481

ER -

Synthesis of Ru-PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions

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Keywords

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