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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.

SUBMITTER: Lau S 

PROVIDER: S-EPMC5684690 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Mild sp<sup>2</sup>Carbon-Oxygen Bond Activation by an Isolable Ruthenium(II) Bis(dinitrogen) Complex: Experiment and Theory.

Lau Samantha S   Ward Bryan B   Zhou Xueer X   White Andrew J P AJP   Casely Ian J IJ   Macgregor Stuart A SA   Crimmin Mark R MR  

Organometallics 20170914 18

The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)<sub>2</sub>(N<sub>2</sub>)<sub>2</sub>(PCy<sub>3</sub>)<sub>2</sub>] (<b>1</b>) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp<sup>2</sup>C-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 brea  ...[more]

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