By the same authors

From the same journal

From the same journal

Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism

Research output: Contribution to journalArticlepeer-review

Standard

Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism. / Perutz, Robin Noel; Jasim, Nasarella A.; Whitwood, Adrian C.; Lledos, Agusti; Ortuno, Manuel.

In: Dalton Transactions, Vol. 45, No. 47, c6dt03241a, 07.10.2016, p. 18842–18850.

Research output: Contribution to journalArticlepeer-review

Harvard

Perutz, RN, Jasim, NA, Whitwood, AC, Lledos, A & Ortuno, M 2016, 'Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism', Dalton Transactions, vol. 45, no. 47, c6dt03241a, pp. 18842–18850. https://doi.org/10.1039/c6dt03241a

APA

Perutz, R. N., Jasim, N. A., Whitwood, A. C., Lledos, A., & Ortuno, M. (2016). Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism. Dalton Transactions, 45(47), 18842–18850. [c6dt03241a]. https://doi.org/10.1039/c6dt03241a

Vancouver

Perutz RN, Jasim NA, Whitwood AC, Lledos A, Ortuno M. Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism. Dalton Transactions. 2016 Oct 7;45(47):18842–18850. c6dt03241a. https://doi.org/10.1039/c6dt03241a

Author

Perutz, Robin Noel ; Jasim, Nasarella A. ; Whitwood, Adrian C. ; Lledos, Agusti ; Ortuno, Manuel. / Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism. In: Dalton Transactions. 2016 ; Vol. 45, No. 47. pp. 18842–18850.

Bibtex - Download

@article{05d256cf0c4d4e6d850988fbe666d6ce,
title = "Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism",
abstract = "A computational study of the C(methyl)–O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp3)2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an SN2 mechanism.Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(II) product trans-[PtMe(OArF)(PCyp3)2]. Structure-reactivity correlations are fully consistentwith this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy3)2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η3-allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy3)2(η3-allyl)][OC5NF4]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.",
author = "Perutz, {Robin Noel} and Jasim, {Nasarella A.} and Whitwood, {Adrian C.} and Agusti Lledos and Manuel Ortuno",
note = " {\textcopyright} The Royal Society of Chemistry 2016. This is an author-produced version of the published paper. Uploaded in accordance with the publisher{\textquoteright}s self-archiving policy. Further copying may not be permitted; contact the publisher for details.",
year = "2016",
month = oct,
day = "7",
doi = "10.1039/c6dt03241a",
language = "English",
volume = "45",
pages = "18842–18850",
journal = "Dalton Transactions",
issn = "1477-9234",
publisher = "Royal Society of Chemistry",
number = "47",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Platinum(0)-mediated C–O bond activation of ethers via an SN2 mechanism

AU - Perutz, Robin Noel

AU - Jasim, Nasarella A.

AU - Whitwood, Adrian C.

AU - Lledos, Agusti

AU - Ortuno, Manuel

N1 - © The Royal Society of Chemistry 2016. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2016/10/7

Y1 - 2016/10/7

N2 - A computational study of the C(methyl)–O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp3)2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an SN2 mechanism.Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(II) product trans-[PtMe(OArF)(PCyp3)2]. Structure-reactivity correlations are fully consistentwith this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy3)2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η3-allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy3)2(η3-allyl)][OC5NF4]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

AB - A computational study of the C(methyl)–O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp3)2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an SN2 mechanism.Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(II) product trans-[PtMe(OArF)(PCyp3)2]. Structure-reactivity correlations are fully consistentwith this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy3)2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η3-allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy3)2(η3-allyl)][OC5NF4]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

UR - http://www.scopus.com/inward/record.url?scp=85000842916&partnerID=8YFLogxK

U2 - 10.1039/c6dt03241a

DO - 10.1039/c6dt03241a

M3 - Article

VL - 45

SP - 18842

EP - 18850

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9234

IS - 47

M1 - c6dt03241a

ER -