From 0 to II in One-Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2

Xiuxiu Yang; Thomas L. Gianetti; Joshua Harbort; Michael D. Wörle; Lilin Tan; Cheng Yong Su; Pascal Jurt; Jeffrey R. Harmer; Hansjörg Grützmacher

doi:10.1002/anie.201605687

From 0 to II in One-Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh₂

Xiuxiu Yang
, Thomas L. Gianetti
, Joshua Harbort
, Michael D. Wörle
, Lilin Tan
, Cheng Yong Su
, Pascal Jurt
, Jeffrey R. Harmer
, Hansjörg Grützmacher

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

13 Scopus citations

Abstract

We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh₂(trop=5-H-dibenzo-[a,d]cyclohepten-5-yl) in the oxidation states 0, +I, and +II, formed via successive one-electron oxidization steps from Ru⁰(tropPPh₂)₂. The bidentate character of the tropPPh₂ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X-ray diffraction analysis. EPR data of the mononuclear Ru^Icomplex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the Ru^Icenter.

Original language	English (US)
Pages (from-to)	11999-12002
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	39
DOIs	https://doi.org/10.1002/anie.201605687
State	Published - Sep 19 2016
Externally published	Yes

Keywords

P ligands
metal radicals
non-redox ligands
one-electron oxidation
ruthenium

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201605687

Cite this

@article{587e12ee5bc74e9e8bf457771189c0a0,

title = "From 0 to II in One-Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2",

abstract = "We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2(trop=5-H-dibenzo-[a,d]cyclohepten-5-yl) in the oxidation states 0, +I, and +II, formed via successive one-electron oxidization steps from Ru0(tropPPh2)2. The bidentate character of the tropPPh2ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X-ray diffraction analysis. EPR data of the mononuclear RuIcomplex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the RuIcenter.",

keywords = "P ligands, metal radicals, non-redox ligands, one-electron oxidation, ruthenium",

author = "Xiuxiu Yang and Gianetti, \{Thomas L.\} and Joshua Harbort and W{\"o}rle, \{Michael D.\} and Lilin Tan and Su, \{Cheng Yong\} and Pascal Jurt and Harmer, \{Jeffrey R.\} and Hansj{\"o}rg Gr{\"u}tzmacher",

note = "Funding Information: This work was financed by the Swiss National Science Foundation (grant 200021 162437/1) and the ETH Z{\"u}rich (grant 2-77230-15). X.Y. is grateful for financial support from the China Scholarship Council, T.L.G. from ETH Z{\"u}rich Postdoctoral Fellowship Program (FEL-14 15-1), and J.R.H. from the ARC (FT120100421) and the Australian National Fabrication Facility for use of equipment. We thank Prof. Dr. Paul S. Pregosin for the helpful discussions on the NMR data of complex 5. Dr. Reinhard Kissner and Dr. Daniel Klose (EPR), Dr. Xiangyang Zhang (HRMS), and Dr. Xiaodan Chen (XRD) are gratefully acknowledged for measurements. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2016",

month = sep,

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doi = "10.1002/anie.201605687",

language = "English (US)",

volume = "55",

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journal = "Angewandte Chemie - International Edition",

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T2 - A Series of Ruthenium Complexes Supported by TropPPh2

AU - Yang, Xiuxiu

AU - Gianetti, Thomas L.

AU - Harbort, Joshua

AU - Wörle, Michael D.

AU - Tan, Lilin

AU - Su, Cheng Yong

AU - Jurt, Pascal

AU - Harmer, Jeffrey R.

AU - Grützmacher, Hansjörg

N1 - Funding Information: This work was financed by the Swiss National Science Foundation (grant 200021 162437/1) and the ETH Zürich (grant 2-77230-15). X.Y. is grateful for financial support from the China Scholarship Council, T.L.G. from ETH Zürich Postdoctoral Fellowship Program (FEL-14 15-1), and J.R.H. from the ARC (FT120100421) and the Australian National Fabrication Facility for use of equipment. We thank Prof. Dr. Paul S. Pregosin for the helpful discussions on the NMR data of complex 5. Dr. Reinhard Kissner and Dr. Daniel Klose (EPR), Dr. Xiangyang Zhang (HRMS), and Dr. Xiaodan Chen (XRD) are gratefully acknowledged for measurements. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2016/9/19

Y1 - 2016/9/19

N2 - We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2(trop=5-H-dibenzo-[a,d]cyclohepten-5-yl) in the oxidation states 0, +I, and +II, formed via successive one-electron oxidization steps from Ru0(tropPPh2)2. The bidentate character of the tropPPh2ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X-ray diffraction analysis. EPR data of the mononuclear RuIcomplex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the RuIcenter.

AB - We report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2(trop=5-H-dibenzo-[a,d]cyclohepten-5-yl) in the oxidation states 0, +I, and +II, formed via successive one-electron oxidization steps from Ru0(tropPPh2)2. The bidentate character of the tropPPh2ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X-ray diffraction analysis. EPR data of the mononuclear RuIcomplex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the RuIcenter.

KW - P ligands

KW - metal radicals

KW - non-redox ligands

KW - one-electron oxidation

KW - ruthenium

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