A High-valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

Shrouq Mujahed; Maria S. Richter; Evgueni Kirillov; Evamarie Hey-Hawkins; Dmitri Gelman

doi:10.1002/ijch.202300037

A High-valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

Shrouq Mujahed, Maria S. Richter, Evgueni Kirillov^*, Evamarie Hey-Hawkins^*, Dmitri Gelman^*

^*Corresponding author for this work

Institute of Chemistry

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

Abstract

In this communication, we report on the successful application of a high-valent Ru^IV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic Ru^IV complex. According to our hypothesis, the positively charged high-valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H₂ bond activation, which leads to efficient catalysis.

Original language	American English
Journal	Israel Journal of Chemistry
DOIs	https://doi.org/10.1002/ijch.202300037
State	Accepted/In press - 2023

Bibliographical note

Funding Information:
This research was supported by GIF (German‐Israeli Foundation for research and development) Grant N I‐1508‐302.5/2019 and by the ISF (Israel Science Foundation) Grant No. 370/20. DG thanks Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. SM thanks the Neubauer Family Foundation for generous financial support. MSR and DG thank Deutscher Akademischer Austauschdienst (DAAD) for generous financial support.

Publisher Copyright:
© 2023 The Authors. Israel Journal of Chemistry published by Wiley-VCH GmbH.

Keywords

cooperative catalysis
high-valent ruthenium
hydrogenation of esters
pincer complexes

Access to Document

10.1002/ijch.202300037

Cite this

@article{b506b416404d46f0888f3f48fc9d56ba,

title = "A High-valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates",

abstract = "In this communication, we report on the successful application of a high-valent RuIV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic RuIV complex. According to our hypothesis, the positively charged high-valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H2 bond activation, which leads to efficient catalysis.",

keywords = "cooperative catalysis, high-valent ruthenium, hydrogenation of esters, pincer complexes",

author = "Shrouq Mujahed and Richter, {Maria S.} and Evgueni Kirillov and Evamarie Hey-Hawkins and Dmitri Gelman",

note = "Funding Information: This research was supported by GIF (German‐Israeli Foundation for research and development) Grant N I‐1508‐302.5/2019 and by the ISF (Israel Science Foundation) Grant No. 370/20. DG thanks Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. SM thanks the Neubauer Family Foundation for generous financial support. MSR and DG thank Deutscher Akademischer Austauschdienst (DAAD) for generous financial support. Publisher Copyright: {\textcopyright} 2023 The Authors. Israel Journal of Chemistry published by Wiley-VCH GmbH.",

year = "2023",

doi = "10.1002/ijch.202300037",

language = "American English",

journal = "Israel Journal of Chemistry",

issn = "0021-2148",

publisher = "Wiley-Blackwell",

}

TY - JOUR

T1 - A High-valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

AU - Mujahed, Shrouq

AU - Richter, Maria S.

AU - Kirillov, Evgueni

AU - Hey-Hawkins, Evamarie

AU - Gelman, Dmitri

N1 - Funding Information: This research was supported by GIF (German‐Israeli Foundation for research and development) Grant N I‐1508‐302.5/2019 and by the ISF (Israel Science Foundation) Grant No. 370/20. DG thanks Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. SM thanks the Neubauer Family Foundation for generous financial support. MSR and DG thank Deutscher Akademischer Austauschdienst (DAAD) for generous financial support. Publisher Copyright: © 2023 The Authors. Israel Journal of Chemistry published by Wiley-VCH GmbH.

PY - 2023

Y1 - 2023

N2 - In this communication, we report on the successful application of a high-valent RuIV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic RuIV complex. According to our hypothesis, the positively charged high-valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H2 bond activation, which leads to efficient catalysis.

AB - In this communication, we report on the successful application of a high-valent RuIV bifunctional catalyst (1) for mild hydrogenation of cyclic and acyclic carbonates. Our experimental and theoretical studies suggest that the hydrogenation mechanism is operated by an unusual formally zwitterionic RuIV complex. According to our hypothesis, the positively charged high-valent metal center is responsible for stronger hydrogen coordination. On the other hand, the proximate negatively charged ligand site facilitates heterolytic H2 bond activation, which leads to efficient catalysis.

KW - cooperative catalysis

KW - high-valent ruthenium

KW - hydrogenation of esters

KW - pincer complexes

UR - http://www.scopus.com/inward/record.url?scp=85151322964&partnerID=8YFLogxK

U2 - 10.1002/ijch.202300037

DO - 10.1002/ijch.202300037

M3 - Article

AN - SCOPUS:85151322964

SN - 0021-2148

JO - Israel Journal of Chemistry

JF - Israel Journal of Chemistry

ER -

A High-valent Ru−PCP Pincer Catalyst for the Hydrogenation of Organic Carbonates

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Fingerprint

Cite this