Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Pascal Jurt; Oleg G. Salnikov; Thomas L. Gianetti; Nikita V. Chukanov; Matthew G. Baker; Grégoire Le Corre; Jaap E. Borger; Rene Verel; Sébastien Gauthier; Olaf Fuhr; Kirill V. Kovtunov; Alexey Fedorov; Dieter Fenske; Igor V. Koptyug; Hansjörg Grützmacher

doi:10.1039/c9sc02683e

Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Pascal Jurt, Oleg G. Salnikov, Thomas L. Gianetti, Nikita V. Chukanov, Matthew G. Baker, Grégoire Le Corre, Jaap E. Borger, Rene Verel, Sébastien Gauthier, Olaf Fuhr, Kirill V. Kovtunov, Alexey Fedorov, Dieter Fenske, Igor V. Koptyug, Hansjörg Grützmacher

Chemistry and Biochemistry

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

11 Scopus citations

Abstract

Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two CC bonds of the trop ligand. This reaction is chemoselective and converts CC bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H₂ activation by interfacial sites of heterogeneous Rh/C catalysts.

Original language	English (US)
Pages (from-to)	7937-7945
Number of pages	9
Journal	Chemical Science
Volume	10
Issue number	34
DOIs	https://doi.org/10.1039/c9sc02683e
State	Published - 2019

ASJC Scopus subject areas

Chemistry(all)

Access to Document

10.1039/c9sc02683e

Cite this

Jurt, P., Salnikov, O. G., Gianetti, T. L., Chukanov, N. V., Baker, M. G., Le Corre, G., Borger, J. E., Verel, R., Gauthier, S., Fuhr, O., Kovtunov, K. V., Fedorov, A., Fenske, D., Koptyug, I. V., & Grützmacher, H. (2019). Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates. Chemical Science, 10(34), 7937-7945. https://doi.org/10.1039/c9sc02683e

Jurt, P, Salnikov, OG, Gianetti, TL, Chukanov, NV, Baker, MG, Le Corre, G, Borger, JE, Verel, R, Gauthier, S, Fuhr, O, Kovtunov, KV, Fedorov, A, Fenske, D, Koptyug, IV & Grützmacher, H 2019, 'Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates', Chemical Science, vol. 10, no. 34, pp. 7937-7945. https://doi.org/10.1039/c9sc02683e

@article{c61a24fef9f0423681c14fb4fa907867,

title = "Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates",

abstract = "Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two CC bonds of the trop ligand. This reaction is chemoselective and converts CC bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H2 activation by interfacial sites of heterogeneous Rh/C catalysts.",

author = "Pascal Jurt and Salnikov, {Oleg G.} and Gianetti, {Thomas L.} and Chukanov, {Nikita V.} and Baker, {Matthew G.} and {Le Corre}, Gr{\'e}goire and Borger, {Jaap E.} and Rene Verel and S{\'e}bastien Gauthier and Olaf Fuhr and Kovtunov, {Kirill V.} and Alexey Fedorov and Dieter Fenske and Koptyug, {Igor V.} and Hansj{\"o}rg Gr{\"u}tzmacher",

note = "Funding Information: We gratefully acknowledge financial support of Swiss National Science Foundation. I. V. K. acknowledges the grant from the Russian Science Foundation (19-13-00172) for the support of hydrogenation experiments with parahydrogen. K. V. K thanks SB RAS integrated research program (# 0333-2018-0006/II.1.13) for parahydrogen activation studies and Ministry of Science and Higher Education of the RF (AAAA-A16-116121510087-5) for access to NMR equipment. A. F. thanks the Holcim Stiftung for the Habilitation fellowship. Funding Information: We gratefully acknowledge nancial support of Swiss National Science Foundation. I. V. K. acknowledges the grant from the Russian Science Foundation (19-13-00172) for the support of hydrogenation experiments with parahydrogen. K. V. K thanks SB RAS integrated research program (# 0333-2018-0006/II.1.13) for parahydrogen activation studies and Ministry of Science and Higher Education of the RF (AAAA-A16-116121510087-5) for access to NMR equipment. A. F. thanks the Holcim Stiung for the Habilitation fellowship. Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c9sc02683e",

language = "English (US)",

volume = "10",

pages = "7937--7945",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "34",

}

TY - JOUR

T1 - Low-valent homobimetallic Rh complexes

T2 - Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

AU - Jurt, Pascal

AU - Salnikov, Oleg G.

AU - Gianetti, Thomas L.

AU - Chukanov, Nikita V.

AU - Baker, Matthew G.

AU - Le Corre, Grégoire

AU - Borger, Jaap E.

AU - Verel, Rene

AU - Gauthier, Sébastien

AU - Fuhr, Olaf

AU - Kovtunov, Kirill V.

AU - Fedorov, Alexey

AU - Fenske, Dieter

AU - Koptyug, Igor V.

AU - Grützmacher, Hansjörg

N1 - Funding Information: We gratefully acknowledge financial support of Swiss National Science Foundation. I. V. K. acknowledges the grant from the Russian Science Foundation (19-13-00172) for the support of hydrogenation experiments with parahydrogen. K. V. K thanks SB RAS integrated research program (# 0333-2018-0006/II.1.13) for parahydrogen activation studies and Ministry of Science and Higher Education of the RF (AAAA-A16-116121510087-5) for access to NMR equipment. A. F. thanks the Holcim Stiftung for the Habilitation fellowship. Funding Information: We gratefully acknowledge nancial support of Swiss National Science Foundation. I. V. K. acknowledges the grant from the Russian Science Foundation (19-13-00172) for the support of hydrogenation experiments with parahydrogen. K. V. K thanks SB RAS integrated research program (# 0333-2018-0006/II.1.13) for parahydrogen activation studies and Ministry of Science and Higher Education of the RF (AAAA-A16-116121510087-5) for access to NMR equipment. A. F. thanks the Holcim Stiung for the Habilitation fellowship. Publisher Copyright: This journal is © The Royal Society of Chemistry.

PY - 2019

Y1 - 2019

N2 - Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two CC bonds of the trop ligand. This reaction is chemoselective and converts CC bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H2 activation by interfacial sites of heterogeneous Rh/C catalysts.

AB - Supporting two metal binding sites by a tailored polydentate trop-based (trop = 5H-dibenzo[a,d]cyclohepten-5-yl) ligand yields highly unsymmetric homobimetallic rhodium(i) complexes. Their reaction with hydrogen rapidly forms Rh hydrides that undergo an intramolecular semihydrogenation of two CC bonds of the trop ligand. This reaction is chemoselective and converts CC bonds to a bridging carbene and an olefinic ligand in the first and the second semihydrogenation steps, respectively. Stabilization by a bridging diphosphine ligand allows characterization of a Rh hydride species by advanced NMR techniques and may provide insight into possible elementary steps of H2 activation by interfacial sites of heterogeneous Rh/C catalysts.

UR - http://www.scopus.com/inward/record.url?scp=85071634082&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85071634082&partnerID=8YFLogxK

U2 - 10.1039/c9sc02683e

DO - 10.1039/c9sc02683e

M3 - Article

AN - SCOPUS:85071634082

SN - 2041-6520

VL - 10

SP - 7937

EP - 7945

JO - Chemical Science

JF - Chemical Science

IS - 34

ER -

Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

CCDC 1919546: Experimental Crystal Structure Determination

CCDC 1919543: Experimental Crystal Structure Determination

CCDC 1919533: Experimental Crystal Structure Determination

Cite this

Low-valent homobimetallic Rh complexes: Influence of ligands on the structure and the intramolecular reactivity of Rh-H intermediates

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1919546: Experimental Crystal Structure Determination

CCDC 1919543: Experimental Crystal Structure Determination

CCDC 1919533: Experimental Crystal Structure Determination

Cite this