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

Institute of Chemical Research of Catalonia

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

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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

Chemistry(all)
Catalysis

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10.1002/anie.201501996

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@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",

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doi = "10.1002/anie.201501996",

language = "English",

volume = "54",

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journal = "Angewandte Chemie International Edition",

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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

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

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Stuart Alan Macgregor

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

Abstract

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