Arylimido‐Bridged Dinuclear Ti(μ‐NAr)<sub>2</sub>Ti Scaffold for Alkyne Insertion into the <i>ortho</i>‐C−H Bond of Arylimido Ligands

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  • Haruki Nagae
    Department of Chemistry Graduate School of Engineering Science, Osaka University, Toyonaka Osaka 560-8531 Japan
  • Wataru Hato
    Department of Chemistry Graduate School of Engineering Science, Osaka University, Toyonaka Osaka 560-8531 Japan
  • Kento Kawakita
    Department of Chemistry Graduate School of Engineering Science, Osaka University, Toyonaka Osaka 560-8531 Japan
  • Hayato Tsurugi
    Department of Chemistry Graduate School of Engineering Science, Osaka University, Toyonaka Osaka 560-8531 Japan
  • Kazushi Mashima
    Department of Chemistry Graduate School of Engineering Science, Osaka University, Toyonaka Osaka 560-8531 Japan

説明

<jats:title>Abstract</jats:title><jats:p>Dinuclear titanium dialkyl complexes bridged by two μ‐arylimido ligands, [CpTi(CH<jats:sub>2</jats:sub>SiMe<jats:sub>3</jats:sub>)(μ‐NAr)]<jats:sub>2</jats:sub> (Cp=cyclopentadienyl) activated an <jats:italic>ortho</jats:italic>‐aryl C−H bond of an μ‐arylimido ligand to form a four‐membered titanacycle. The subsequent insertion reaction of 1‐(trimethylsilyl)propyne into a metal–carbon bond of the four‐membered titanacycle yielded the corresponding six‐membered titanacycle. Further <jats:italic>ortho</jats:italic>‐C−H bond activation of the other μ‐arylimido ligand and an insertion reaction proceeded to give dinuclear titanium complexes with two six‐membered titanacycles. An Eyring plot in the temperature range 130–150 °C revealed activation parameters for the alkenylation reaction, and deuterium‐labeling experiments showed that the C−H bond activation step is the rate determining step. Relative Gibbs free energies of the starting complexes, reaction intermediates, and transition states were calculated by using DFT calculations.</jats:p>

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