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- W2754182904 abstract "Abstract The reaction of an oxime ester with [Ru(PPh 3 ) 3 X 2 ] proceeded smoothly at room temperature to afford a stable Ru IV ketimido complex as oxidative adduct. The structure of the complex was unambiguously determined by X‐ray crystallographic analysis, which showed an almost linear Ru−N−C array. The electronic properties of the nitrogen atom were estimated by DFT calculations, and the results suggested double‐bond character of the Ru−N bond. Kinetic studies and consideration of the substituent effect on the oxime ester led to the proposal of a reaction mechanism involving oxidative addition, which could proceed by N,O‐chelating coordination to the Ru center prior to N−O bond cleavage. The obtained Ru ketimido complex could be transformed into a ruthenacycle by C−H activation by a concerted metalation–deprotonation mechanism in dichloromethane/methanol. Ru ketimido complexes with a tethered alkyne or alkene moiety underwent chloroamination of unsaturated C−C bonds followed by C−H activation, which resulted in the formation of a ruthenacycle. Considering the LUMO of an isolated Ru ketimido complex, the chloroamination should proceed by a synchronous 1,3‐dipolar cycloaddition‐type mechanism. Insight into the character and reactivity of Ru ketimido complexes will be helpful for developments in the catalytic transformation of oxime esters." @default.
- W2754182904 created "2017-09-25" @default.
- W2754182904 creator A5019138873 @default.
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- W2754182904 date "2017-11-07" @default.
- W2754182904 modified "2023-10-09" @default.
- W2754182904 title "Generation of Stable Ruthenium(IV) Ketimido Complexes by Oxidative Addition of Oxime Esters to Ruthenium(II): Reactivity Studies Based on Electronic Properties of the Ru−N Bond" @default.
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- W2754182904 doi "https://doi.org/10.1002/chem.201704102" @default.
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