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

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Title: Mild sp2Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) bis(Dinitrogen) Complex: Experiment and Theory
Authors: Crimmin, MR
Lau, S
Ward, B
White, AJP
Macgregor, SA
Casely, IJ
Item Type: Journal Article
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.
Issue Date: 14-Sep-2017
Date of Acceptance: 14-Sep-2017
URI: http://hdl.handle.net/10044/1/51845
DOI: https://dx.doi.org/10.1021/acs.organomet.7b00632
ISSN: 0276-7333
Publisher: American Chemical Society
Start Page: 3654
End Page: 3663
Journal / Book Title: Organometallics
Volume: 36
Issue: 18
Copyright Statement: ACS AuthorChoice - This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License, which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.
Sponsor/Funder: The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Commission of the European Communities
Funder's Grant Number: UF090149
EP/L011514/1
677367
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Chemistry
C-O BONDS
DENSITY-FUNCTIONAL THEORY
TRANSITION-METAL CENTERS
CARBON-HYDROGEN BONDS
ARYL ETHERS
BASIS-SETS
COUPLING REACTION
OXYGEN BOND
POLARIZATION FUNCTIONS
REDUCTIVE CLEAVAGE
0302 Inorganic Chemistry
0305 Organic Chemistry
0399 Other Chemical Sciences
Organic Chemistry
Publication Status: Published
Appears in Collections:Chemistry
Faculty of Natural Sciences



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