Radical-chain oxidative addition mechanism for the reaction of an [Re(CO)5]− anion with α-bromostilbene†
Abstract
CHPh}] and Na[Re2(CO)9{Z-C(Ph)
CHPh}] as the main products.
CHPh}] and its complete transformation into Na[Re2(CO)9{Z-C(Ph)
CHPh}]. Treatment of Na[ReBr(CO)4{Z-C(Ph)
CHPh}] with CO almost quantitatively converts it to [Re(CO)5{Z-C(Ph)
CHPh}], the structure of which is established by a single-crystal X-ray diffraction study. A radical-chain mechanism is proposed for the reaction comprising the following steps: (a) coupling of a Vin˙ radical with Na[Re(CO)5], (b) CO-dissociation from the formed 19-electron radical-anion and (c) bromine atom abstraction by [Re(CO)4{Z-C(Ph)
CHPh}]˙− from
CHPh}] product in the presence of NaI. When the radical-chain process is inhibited, a slow halogenophilic reaction is observed, mainly giving the Z and E-isomers of the acylrhenate Na[Re2(CO)9{C(O)C(Ph)
CHPh}].
- This article is part of the themed collection: Mechanistic Organometallic Chemistry