Mild sp2Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory

Samantha Lau; Bryan Ward; Xueer Zhou; Andrew J. P. White; Ian J. Casely; Stuart Alan Macgregor; Mark R. Crimmin

doi:10.1021/acs.organomet.7b00632

Mild sp²Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory

Samantha Lau, Bryan Ward, Xueer Zhou, Andrew J. P. White, Ian J. Casely^*, Stuart Alan Macgregor, Mark R. Crimmin

^*Corresponding author for this work

Imperial College London

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

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Abstract

The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)₂(N₂)₂(PCy₃)₂] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp²C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors. Both experimentally and by DFT calculations, sp²C-H bond activation is shown to be more facile than sp²C-O bond activation. The kinetic preference for C-H bond activation over C-O activation is attributed to unfavorable approach of the C-O bond toward the metal in the selectivity determining step of the reaction pathway.

Original language	English
Pages (from-to)	3654-3663
Number of pages	10
Journal	Organometallics
Volume	36
Issue number	18
Early online date	14 Sept 2017
DOIs	https://doi.org/10.1021/acs.organomet.7b00632
Publication status	Published - 25 Sept 2017

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Mild sp2Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory",

abstract = "The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp2C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors. Both experimentally and by DFT calculations, sp2C-H bond activation is shown to be more facile than sp2C-O bond activation. The kinetic preference for C-H bond activation over C-O activation is attributed to unfavorable approach of the C-O bond toward the metal in the selectivity determining step of the reaction pathway.",

author = "Samantha Lau and Bryan Ward and Xueer Zhou and White, {Andrew J. P.} and Casely, {Ian J.} and Macgregor, {Stuart Alan} and Crimmin, {Mark R.}",

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AU - Ward, Bryan

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AU - White, Andrew J. P.

AU - Casely, Ian J.

AU - Macgregor, Stuart Alan

AU - Crimmin, Mark R.

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N2 - The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp2C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors. Both experimentally and by DFT calculations, sp2C-H bond activation is shown to be more facile than sp2C-O bond activation. The kinetic preference for C-H bond activation over C-O activation is attributed to unfavorable approach of the C-O bond toward the metal in the selectivity determining step of the reaction pathway.

AB - The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp2C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors. Both experimentally and by DFT calculations, sp2C-H bond activation is shown to be more facile than sp2C-O bond activation. The kinetic preference for C-H bond activation over C-O activation is attributed to unfavorable approach of the C-O bond toward the metal in the selectivity determining step of the reaction pathway.

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Mild sp²Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory

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