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

Isfahan University of Technology
Technical University of Munich

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

7 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",

volume = "979",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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TY - JOUR

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

UR - https://www.scopus.com/pages/publications/85137299788

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

Abstract

Keywords

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