論文

査読有り
2017年11月

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

CHEMISTRY-A EUROPEAN JOURNAL
  • Takuya Shimbayashi
  • ,
  • Kazuhiro Okamoto
  • ,
  • Kouichi Ohe

23
66
開始ページ
16892
終了ページ
16897
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1002/chem.201704102
出版者・発行元
WILEY-V C H VERLAG GMBH

The reaction of an oxime ester with [Ru(PPh3)(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.

Web of Science ® 被引用回数 : 6

リンク情報
DOI
https://doi.org/10.1002/chem.201704102
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000416549200028&DestApp=WOS_CPL

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