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

Research output: Contribution to journalArticlepeer-review

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Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II) : Arresting kinetics, autocatalysis, and mechanisms. / Miloserdov, Fedor M.; McKay, David; Muñoz, Bianca K.; Samouei, Hamidreza; Macgregor, Stuart A.; Grushin, Vladimir V.

In: Angewandte Chemie International Edition, Vol. 54, No. 29, 02.06.2015, p. 8466–8470.

Research output: Contribution to journalArticlepeer-review

Harvard

Miloserdov, FM, McKay, D, Muñoz, BK, Samouei, H, Macgregor, SA & Grushin, VV 2015, 'Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms', Angewandte Chemie International Edition, vol. 54, no. 29, pp. 8466–8470. https://doi.org/10.1002/anie.201501996

APA

Miloserdov, F. M., McKay, D., Muñoz, B. K., Samouei, H., Macgregor, S. A., & Grushin, V. V. (2015). Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms. Angewandte Chemie International Edition, 54(29), 8466–8470. https://doi.org/10.1002/anie.201501996

Vancouver

Miloserdov FM, McKay D, Muñoz BK, Samouei H, Macgregor SA, Grushin VV. Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II): Arresting kinetics, autocatalysis, and mechanisms. Angewandte Chemie International Edition. 2015 Jun 2;54(29):8466–8470. https://doi.org/10.1002/anie.201501996

Author

Miloserdov, Fedor M. ; McKay, David ; Muñoz, Bianca K. ; Samouei, Hamidreza ; Macgregor, Stuart A. ; Grushin, Vladimir V. / Exceedingly facile Ph−X activation (X=Cl, Br, I) with ruthenium(II) : Arresting kinetics, autocatalysis, and mechanisms. In: Angewandte Chemie International Edition. 2015 ; Vol. 54, No. 29. pp. 8466–8470.

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@article{3715a4cfe90a4a2a8579090fb7b94859,
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[BOND]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[BOND]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[BOND]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 = "The ICIQ Foundation and The Spanish Government (Grant CTQ2011-25418 and the Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319) are thankfully acknowledged for support of this work. F.M.M. is grateful to the Government of Spain (MICINN) for the FPI Ph.D. Scholarship (BES-2012-054922). S.A.M. and D.M. thank the EPSRC for support through award EP/J010677/1.",
year = "2015",
month = jun,
day = "2",
doi = "10.1002/anie.201501996",
language = "English",
volume = "54",
pages = "8466–8470",
journal = "Angewandte Chemie International Edition",
issn = "1433-7851",
publisher = "John Wiley & Sons, Ltd.",
number = "29",

}

RIS (suitable for import to EndNote) - Download

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 - The ICIQ Foundation and The Spanish Government (Grant CTQ2011-25418 and the Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319) are thankfully acknowledged for support of this work. F.M.M. is grateful to the Government of Spain (MICINN) for the FPI Ph.D. Scholarship (BES-2012-054922). S.A.M. and D.M. thank the EPSRC for support through award EP/J010677/1.

PY - 2015/6/2

Y1 - 2015/6/2

N2 - [(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph[BOND]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[BOND]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[BOND]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[BOND]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[BOND]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[BOND]I oxidative addition.

KW - Ar-X activation

KW - autocatalysis

KW - DFT calculations

KW - kinetics

KW - ruthenium

UR - http://dx.doi.org/10.1002/anie.201501996

U2 - 10.1002/anie.201501996

DO - 10.1002/anie.201501996

M3 - Article

VL - 54

SP - 8466

EP - 8470

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 29

ER -

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