N-heterocyclic carbene complexes of Rh: Reaction with dioxygen without oxidation

Jeremy M. Praetorius; Daryl P. Allen; Ruiyao Wang; Jonathan D. Webb; Friedrich Grein; Pierre Kennepohl; Cathleen M. Crudden

doi:10.1021/ja7108213

N-heterocyclic carbene complexes of Rh: Reaction with dioxygen without oxidation

Jeremy M. Praetorius, Daryl P. Allen, Ruiyao Wang, Jonathan D. Webb, Friedrich Grein, Pierre Kennepohl^*, Cathleen M. Crudden

^*Corresponding author for this work

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

68 Citations (Scopus)

Abstract

The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d⁸ metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 Å range.

Original language	English
Pages (from-to)	3724-3725
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	130
Issue number	12
DOIs	https://doi.org/10.1021/ja7108213
Publication status	Published - 26 Mar 2008
Externally published	Yes

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Praetorius, J. M., Allen, D. P., Wang, R., Webb, J. D., Grein, F., Kennepohl, P., & Crudden, C. M. (2008). N-heterocyclic carbene complexes of Rh: Reaction with dioxygen without oxidation. Journal of the American Chemical Society, 130(12), 3724-3725. https://doi.org/10.1021/ja7108213

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abstract = "The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d8 metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 {\AA} range.",

author = "Praetorius, {Jeremy M.} and Allen, {Daryl P.} and Ruiyao Wang and Webb, {Jonathan D.} and Friedrich Grein and Pierre Kennepohl and Crudden, {Cathleen M.}",

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doi = "10.1021/ja7108213",

language = "English",

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T2 - Reaction with dioxygen without oxidation

AU - Praetorius, Jeremy M.

AU - Allen, Daryl P.

AU - Wang, Ruiyao

AU - Webb, Jonathan D.

AU - Grein, Friedrich

AU - Kennepohl, Pierre

AU - Crudden, Cathleen M.

PY - 2008/3/26

Y1 - 2008/3/26

N2 - The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d8 metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 Å range.

AB - The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d8 metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 Å range.

UR - http://www.scopus.com/inward/record.url?scp=41149178574&partnerID=8YFLogxK

U2 - 10.1021/ja7108213

DO - 10.1021/ja7108213

M3 - Article

C2 - 18321109

AN - SCOPUS:41149178574

SN - 0002-7863

VL - 130

SP - 3724

EP - 3725

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 12

ER -

N-heterocyclic carbene complexes of Rh: Reaction with dioxygen without oxidation

Abstract

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