Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations

Jørn Hansen; Bo Li; Evgeny Dikarev; Jochen Autschbach; Huw M.L. Davies

doi:10.1021/jo900998s

Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations

Jørn Hansen
, Bo Li
, Evgeny Dikarev
, Jochen Autschbach
, Huw M.L. Davies

Chemistry

Emory University
SUNY Albany

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

67 Scopus citations

Abstract

(Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O₂CCF₃)₃(O₂CCH₃) was found to be approximately 1600 times less reactive than its homometallic analogue Rh₂(O₂CCF₃)₃(O ₂CCH₃) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.

Original language	English
Pages (from-to)	6564-6571
Number of pages	8
Journal	Journal of Organic Chemistry
Volume	74
Issue number	17
DOIs	https://doi.org/10.1021/jo900998s
State	Published - Sep 4 2009

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title = "Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations",

abstract = "(Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O2CCF3)3(O2CCH3) was found to be approximately 1600 times less reactive than its homometallic analogue Rh2(O2CCF3)3(O 2CCH3) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.",

author = "J{\o}rn Hansen and Bo Li and Evgeny Dikarev and Jochen Autschbach and Davies, \{Huw M.L.\}",

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TY - JOUR

T1 - Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations

AU - Hansen, Jørn

AU - Li, Bo

AU - Dikarev, Evgeny

AU - Autschbach, Jochen

AU - Davies, Huw M.L.

PY - 2009/9/4

Y1 - 2009/9/4

N2 - (Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O2CCF3)3(O2CCH3) was found to be approximately 1600 times less reactive than its homometallic analogue Rh2(O2CCF3)3(O 2CCH3) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.

AB - (Chemical Equation Presented) The catalytic activity of heterobimetallic Bi-Rh paddlewheel carboxylate complexes has been evaluated for the first time in the context of metal carbenoid chemistry. The Bi-Rh carboxylate complexes were found to effectively catalyze both cyclopropanation reactions and C-H insertions as well as reactions involving ylide intermediates with similar selectivity profiles to analogous dirhodium complexes. The heterometallic complex BiRh(O2CCF3)3(O2CCH3) was found to be approximately 1600 times less reactive than its homometallic analogue Rh2(O2CCF3)3(O 2CCH3) toward the decomposition of methyl phenyldiazoacetate. The observed difference in reactivity is in good agreement with a computational model system where axial coordination to the second rhodium active site is considered for the dirhodium catalyst.

UR - https://www.scopus.com/pages/publications/69549096246

U2 - 10.1021/jo900998s

DO - 10.1021/jo900998s

M3 - Article

AN - SCOPUS:69549096246

SN - 0022-3263

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SP - 6564

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 17

ER -

Combined experimental and computational studies of heterobimetallic Bi-Rh paddlewheel carboxylates as catalysts for metal carbenoid transformations

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