Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex

Katherine P. Kornecki; John F. Briones; Vyacheslav Boyarskikh; Felicia Fullilove; Jochen Autschbach; Kaitlin E. Schrote; Kyle M. Lancaster; Huw M.L. Davies; John F. Berry

doi:10.1126/science.1243200

Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex

Katherine P. Kornecki
, John F. Briones
, Vyacheslav Boyarskikh
, Felicia Fullilove
, Jochen Autschbach
, Kaitlin E. Schrote
, Kyle M. Lancaster
, Huw M.L. Davies
, John F. Berry

Chemistry

University of Wisconsin-Madison
Emory University
Cornell University

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

185 Scopus citations

Abstract

A multitude of organic transformations catalyzed by dirhodium(II) (Rh ₂) complexes are thought to proceed via the intermediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observation. Herein, we report the generation of a metastable Rh ₂-carbenoid intermediate supported by a donor-acceptor carbene fragment. This intermediate is stable for a period of ∼20 hours in chloroform solution at 0°C, allowing for an exploration of its physical and chemical properties. The Rh=C bond, characterized by vibrational and nuclear magnetic resonance spectroscopy, extended x-ray absorption fine structure analysis, and quantum-chemical calculations, has weak σ and π components. This intermediate performs stoichiometric cyclopropanation and C-H functionalization reactions to give products that are identical to those obtained from analogous Rh₂ catalysis.

Original language	English
Pages (from-to)	351-354
Number of pages	4
Journal	Science
Volume	342
Issue number	6156
DOIs	https://doi.org/10.1126/science.1243200
State	Published - 2013

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title = "Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex",

abstract = "A multitude of organic transformations catalyzed by dirhodium(II) (Rh 2) complexes are thought to proceed via the intermediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observation. Herein, we report the generation of a metastable Rh 2-carbenoid intermediate supported by a donor-acceptor carbene fragment. This intermediate is stable for a period of ∼20 hours in chloroform solution at 0°C, allowing for an exploration of its physical and chemical properties. The Rh=C bond, characterized by vibrational and nuclear magnetic resonance spectroscopy, extended x-ray absorption fine structure analysis, and quantum-chemical calculations, has weak σ and π components. This intermediate performs stoichiometric cyclopropanation and C-H functionalization reactions to give products that are identical to those obtained from analogous Rh2 catalysis.",

author = "Kornecki, \{Katherine P.\} and Briones, \{John F.\} and Vyacheslav Boyarskikh and Felicia Fullilove and Jochen Autschbach and Schrote, \{Kaitlin E.\} and Lancaster, \{Kyle M.\} and Davies, \{Huw M.L.\} and Berry, \{John F.\}",

year = "2013",

doi = "10.1126/science.1243200",

language = "English",

volume = "342",

pages = "351--354",

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TY - JOUR

T1 - Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex

AU - Kornecki, Katherine P.

AU - Briones, John F.

AU - Boyarskikh, Vyacheslav

AU - Fullilove, Felicia

AU - Autschbach, Jochen

AU - Schrote, Kaitlin E.

AU - Lancaster, Kyle M.

AU - Davies, Huw M.L.

AU - Berry, John F.

PY - 2013

Y1 - 2013

N2 - A multitude of organic transformations catalyzed by dirhodium(II) (Rh 2) complexes are thought to proceed via the intermediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observation. Herein, we report the generation of a metastable Rh 2-carbenoid intermediate supported by a donor-acceptor carbene fragment. This intermediate is stable for a period of ∼20 hours in chloroform solution at 0°C, allowing for an exploration of its physical and chemical properties. The Rh=C bond, characterized by vibrational and nuclear magnetic resonance spectroscopy, extended x-ray absorption fine structure analysis, and quantum-chemical calculations, has weak σ and π components. This intermediate performs stoichiometric cyclopropanation and C-H functionalization reactions to give products that are identical to those obtained from analogous Rh2 catalysis.

AB - A multitude of organic transformations catalyzed by dirhodium(II) (Rh 2) complexes are thought to proceed via the intermediacy of highly reactive, electrophilic carbenoid intermediates that have eluded direct observation. Herein, we report the generation of a metastable Rh 2-carbenoid intermediate supported by a donor-acceptor carbene fragment. This intermediate is stable for a period of ∼20 hours in chloroform solution at 0°C, allowing for an exploration of its physical and chemical properties. The Rh=C bond, characterized by vibrational and nuclear magnetic resonance spectroscopy, extended x-ray absorption fine structure analysis, and quantum-chemical calculations, has weak σ and π components. This intermediate performs stoichiometric cyclopropanation and C-H functionalization reactions to give products that are identical to those obtained from analogous Rh2 catalysis.

UR - https://www.scopus.com/pages/publications/84885838447

U2 - 10.1126/science.1243200

DO - 10.1126/science.1243200

M3 - Article

AN - SCOPUS:84885838447

SN - 0036-8075

VL - 342

SP - 351

EP - 354

JO - Science

JF - Science

IS - 6156

ER -

Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex

Abstract

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