Exceedingly facile Ph-X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms

Fedor M. Miloserdov; David Mckay; Bianca K. Muñoz; Hamidreza Samouei; Stuart A. Macgregor; Vladimir V. Grushin

doi:10.1002/anie.201501996

Exceedingly facile Ph-X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms

Fedor M. Miloserdov
, David Mckay
, Bianca K. Muñoz
, Hamidreza Samouei
, Stuart A. Macgregor
, Vladimir V. Grushin^*

^*Corresponding author for this work

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

20 Citations (Scopus)

112 Downloads (Pure)

Abstract

[(Ph₃P)₃Ru(L)(H)₂] (where L=H₂ (1) in the presence of styrene, Ph₃P (3), and N₂ (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph₃P)₃RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph₃P)₃Ru(H)₂] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph₃P)₂RuI₂], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh₃ dissociation, PhI coordination to Ru through I, rearrangement to a η²-PhI intermediate, and Ph-I oxidative addition.

Original language	English
Pages (from-to)	8466–8470
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	54
Issue number	29
Early online date	2 Jun 2015
DOIs	https://doi.org/10.1002/anie.201501996
Publication status	Published - 13 Jul 2015

Keywords

Ar-X activation
Autocatalysis
DFT calculations
Kinetics
Ruthenium

ASJC Scopus subject areas

General Chemistry
Catalysis

Access to Document

10.1002/anie.201501996

Download pdf
© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 790 KBLicence: Creative Commons: Attribution (CC-BY)

Cite this

@article{c75ef3982c0a498dbed5e5ccbf19cacb,

title = "Exceedingly facile Ph-X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms",

abstract = "[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph-I oxidative addition.",

keywords = "Ar-X activation, Autocatalysis, DFT calculations, Kinetics, Ruthenium",

author = "Miloserdov, \{Fedor M.\} and David Mckay and Mu{\~n}oz, \{Bianca K.\} and Hamidreza Samouei and Macgregor, \{Stuart A.\} and Grushin, \{Vladimir V.\}",

note = "{"}S.A.M. and D.M. thank the EPSRC for support through award EP/J010677/1.{"}",

year = "2015",

month = jul,

day = "13",

doi = "10.1002/anie.201501996",

language = "English",

volume = "54",

pages = "8466–8470",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "Wiley",

number = "29",

}

TY - JOUR

T1 - Exceedingly facile Ph-X activation (X=Cl, Br, I) with ruthenium(II)

T2 - Arresting kinetics, autocatalysis, and mechanisms

AU - Miloserdov, Fedor M.

AU - Mckay, David

AU - Muñoz, Bianca K.

AU - Samouei, Hamidreza

AU - Macgregor, Stuart A.

AU - Grushin, Vladimir V.

N1 - "S.A.M. and D.M. thank the EPSRC for support through award EP/J010677/1."

PY - 2015/7/13

Y1 - 2015/7/13

N2 - [(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph-I oxidative addition.

AB - [(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph-I oxidative addition.

KW - Ar-X activation

KW - Autocatalysis

KW - DFT calculations

KW - Kinetics

KW - Ruthenium

UR - https://www.scopus.com/pages/publications/84947864322

U2 - 10.1002/anie.201501996

DO - 10.1002/anie.201501996

M3 - Article

C2 - 26036691

SN - 1433-7851

VL - 54

SP - 8466

EP - 8470

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 29

ER -

Exceedingly facile Ph-X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this