Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway

Mateusz K. Cybulski; David McKay; Stuart A. Macgregor; Mary F. Mahon; Michael K. Whittlesey

doi:10.1002/anie.201610820

Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway

Mateusz K. Cybulski
, David McKay
, Stuart A. Macgregor
, Mary F. Mahon
, Michael K. Whittlesey

School of Chemistry

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

Abstract

The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe₄)₄H₂] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

Original language	English
Pages (from-to)	1515-1519
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	56
Issue number	6
Early online date	9 Jan 2017
DOIs	https://doi.org/10.1002/anie.201610820
Publication status	Published - 1 Feb 2017

Keywords

Density functional calculations
Homogeneous catalysis
Hydrodefluorination
N-heterocyclic carbenes
Ruthenium

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10.1002/anie.201610820

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© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/anie.201610820
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title = "Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway",

abstract = "The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4)4H2] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.",

keywords = "Density functional calculations, Homogeneous catalysis, Hydrodefluorination, N-heterocyclic carbenes, Ruthenium",

author = "Cybulski, \{Mateusz K.\} and David McKay and Macgregor, \{Stuart A.\} and Mahon, \{Mary F.\} and Whittlesey, \{Michael K.\}",

note = "The authors acknowledge the EPSRC (grant EP/J009962/1, DTA) for financial support ",

year = "2017",

month = feb,

day = "1",

doi = "10.1002/anie.201610820",

language = "English",

volume = "56",

pages = "1515--1519",

journal = "Angewandte Chemie International Edition",

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Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway. / Cybulski, Mateusz K.; McKay, David; Macgregor, Stuart A. et al.
In: Angewandte Chemie International Edition, Vol. 56, No. 6, 01.02.2017, p. 1515-1519.

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

TY - JOUR

T1 - Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway

AU - Cybulski, Mateusz K.

AU - McKay, David

AU - Macgregor, Stuart A.

AU - Mahon, Mary F.

AU - Whittlesey, Michael K.

N1 - The authors acknowledge the EPSRC (grant EP/J009962/1, DTA) for financial support

PY - 2017/2/1

Y1 - 2017/2/1

N2 - The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4)4H2] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

AB - The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe4)4H2] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

KW - Density functional calculations

KW - Homogeneous catalysis

KW - Hydrodefluorination

KW - N-heterocyclic carbenes

KW - Ruthenium

UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201610820/abstract#footer-support-info

U2 - 10.1002/anie.201610820

DO - 10.1002/anie.201610820

M3 - Article

SN - 1521-3773

VL - 56

SP - 1515

EP - 1519

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 6

ER -

Room temperature regioselective catalytic hydrodefluorination of fluoroarenes with trans-[Ru(NHC)4H2] through a concerted nucleophilic Ru−H attack pathway

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