Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation

Mohammad Kaikhosravi; Alexander D. Böth; Michael J. Sauer; Robert M. Reich; Fritz E. Kühn

doi:10.1016/j.jorganchem.2022.122498

Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation

Mohammad Kaikhosravi, Alexander D. Böth, Michael J. Sauer, Robert M. Reich, Fritz E. Kühn

Associate Professorship of Molecular Catalysis

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

6 Scopus citations

Abstract

The heterobimetallic N-heterocyclic dicarbene (NHDC) rhodium ruthenium complex [Ru(OAc)(Mes-NHC-methyl-PPh₂)(Mes-aNHC-methyl-PPh₂)RhCl(cod)] (4) is obtained from a mixed normal/abnormal bis-NHC ruthenium complex via transmetallation by addition of [RhCl(cod)]₂ in THF at 40 °C, applying Ag₂O as base. Crystallization is achieved by layering a solution of 4 in THF with Et₂O. The complex is applicable as a catalyst in the transfer hydrogenation (TH) reaction of acetophenone, exhibiting a turnover frequency (TOF) of 6 700 h⁻¹ with 80% conversion after 25 min (0.10 mol% catalyst, ⁱPrOH, 80 °C, 2.00 mol% NaⁱOPr). These results are compared to an analogous iridium ruthenium NHDC complex.

Original language	English
Article number	122498
Journal	Journal of Organometallic Chemistry
Volume	979
DOIs	https://doi.org/10.1016/j.jorganchem.2022.122498
State	Published - 15 Nov 2022

Keywords

Abnormal N-heterocyclic carbene
Crystal structure
Heterobimetallic
Rhodium
Ruthenium
Transfer hydrogenation

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10.1016/j.jorganchem.2022.122498

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@article{8eb6486812304b98a88e385e77bf0202,

title = "Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation",

abstract = "The heterobimetallic N-heterocyclic dicarbene (NHDC) rhodium ruthenium complex [Ru(OAc)(Mes-NHC-methyl-PPh2)(Mes-aNHC-methyl-PPh2)RhCl(cod)] (4) is obtained from a mixed normal/abnormal bis-NHC ruthenium complex via transmetallation by addition of [RhCl(cod)]2 in THF at 40 °C, applying Ag2O as base. Crystallization is achieved by layering a solution of 4 in THF with Et2O. The complex is applicable as a catalyst in the transfer hydrogenation (TH) reaction of acetophenone, exhibiting a turnover frequency (TOF) of 6 700 h−1 with 80% conversion after 25 min (0.10 mol% catalyst, iPrOH, 80 °C, 2.00 mol% NaiOPr). These results are compared to an analogous iridium ruthenium NHDC complex.",

keywords = "Abnormal N-heterocyclic carbene, Crystal structure, Heterobimetallic, Rhodium, Ruthenium, Transfer hydrogenation",

author = "Mohammad Kaikhosravi and B{\"o}th, {Alexander D.} and Sauer, {Michael J.} and Reich, {Robert M.} and K{\"u}hn, {Fritz E.}",

note = "Publisher Copyright: {\textcopyright} 2022 Elsevier B.V.",

year = "2022",

month = nov,

day = "15",

doi = "10.1016/j.jorganchem.2022.122498",

language = "English",

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journal = "Journal of Organometallic Chemistry",

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T1 - Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation

AU - Kaikhosravi, Mohammad

AU - Böth, Alexander D.

AU - Sauer, Michael J.

AU - Reich, Robert M.

AU - Kühn, Fritz E.

PY - 2022/11/15

Y1 - 2022/11/15

N2 - The heterobimetallic N-heterocyclic dicarbene (NHDC) rhodium ruthenium complex [Ru(OAc)(Mes-NHC-methyl-PPh2)(Mes-aNHC-methyl-PPh2)RhCl(cod)] (4) is obtained from a mixed normal/abnormal bis-NHC ruthenium complex via transmetallation by addition of [RhCl(cod)]2 in THF at 40 °C, applying Ag2O as base. Crystallization is achieved by layering a solution of 4 in THF with Et2O. The complex is applicable as a catalyst in the transfer hydrogenation (TH) reaction of acetophenone, exhibiting a turnover frequency (TOF) of 6 700 h−1 with 80% conversion after 25 min (0.10 mol% catalyst, iPrOH, 80 °C, 2.00 mol% NaiOPr). These results are compared to an analogous iridium ruthenium NHDC complex.

AB - The heterobimetallic N-heterocyclic dicarbene (NHDC) rhodium ruthenium complex [Ru(OAc)(Mes-NHC-methyl-PPh2)(Mes-aNHC-methyl-PPh2)RhCl(cod)] (4) is obtained from a mixed normal/abnormal bis-NHC ruthenium complex via transmetallation by addition of [RhCl(cod)]2 in THF at 40 °C, applying Ag2O as base. Crystallization is achieved by layering a solution of 4 in THF with Et2O. The complex is applicable as a catalyst in the transfer hydrogenation (TH) reaction of acetophenone, exhibiting a turnover frequency (TOF) of 6 700 h−1 with 80% conversion after 25 min (0.10 mol% catalyst, iPrOH, 80 °C, 2.00 mol% NaiOPr). These results are compared to an analogous iridium ruthenium NHDC complex.

KW - Abnormal N-heterocyclic carbene

KW - Crystal structure

KW - Heterobimetallic

KW - Rhodium

KW - Ruthenium

KW - Transfer hydrogenation

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U2 - 10.1016/j.jorganchem.2022.122498

DO - 10.1016/j.jorganchem.2022.122498

M3 - Article

AN - SCOPUS:85137299788

SN - 0022-328X

VL - 979

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

M1 - 122498

ER -

Synthesis and Characterisation of a Heterobimetallic N-heterocyclic Carbene Rhodium Ruthenium Complex as Catalyst for Transfer Hydrogenation

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Keywords

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