Olefin epoxidation by mono and bisperoxo complexes of Mo(VI): a density functional model study

✍ Scribed by Ilya V. Yudanov; Cristiana Di Valentin; Philip Gisdakis; Notker Rösch

• Publisher: Elsevier Science
• Year: 2000
• Tongue: English
• Weight: 133 KB
• Volume: 158
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/s1381-1169(00)00065-0

✦ Synopsis

¨Ä bstract Ž . Ž . Olefin epoxidation by Mo VI peroxo complexes was computationally investigated DFT B3LYP for various monoper-Ž .Ž .Ž . Ž . oxo models X MoO O H O NH with anionic ligands X and for the experimentally known complex MoO O 2 2 2 3 2 Ž .Ž . dipic H O . All these monoperoxo complexes exhibit higher barriers for direct oxygen transfer to ethylene than the 2 Ž . Ž .Ž . reference bisperoxo complex MoO O H O NH with the same base ligand configuration; the most electronegative 2 2 2 3

ligands X induce the lowest barriers. A molecular orbital analysis reveals factors that govern the activity of the peroxo ligand and corroborates the electrophilic character of the attack of a peroxo group on the olefin.