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 A. 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 A. MacGregor, Mark R. Crimmin

^*Corresponding author for this work

School of Chemistry

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

12 Citations (Scopus)

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
DOIs	https://doi.org/10.1021/acs.organomet.7b00632
Publication status	Published - 25 Sept 2017

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10.1021/acs.organomet.7b00632

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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 A.} and Crimmin, {Mark R.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.organomet.7b00632",

language = "English",

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T1 - Mild sp2Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex

T2 - Experiment and Theory

AU - Lau, Samantha

AU - Ward, Bryan

AU - Zhou, Xueer

AU - White, Andrew J.P.

AU - Casely, Ian J.

AU - MacGregor, Stuart A.

AU - Crimmin, Mark R.

PY - 2017/9/25

Y1 - 2017/9/25

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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DO - 10.1021/acs.organomet.7b00632

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SN - 0276-7333

VL - 36

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JO - Organometallics

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IS - 18

ER -

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

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CCDC 1530724 - 1530730: Experimental Crystal Structure Determination

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

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CCDC 1530724 - 1530730: Experimental Crystal Structure Determination

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