title: Mechanism for the activation of carbon monoxide via oxorhenium complexes.
abstract: Activation of CO by the rhenium(V) oxo complex [(DAAm)Re(O)(CH(3))] (1) [DAAm = N,N-bis(2-arylaminoethyl)methylamine; aryl = C(6)F(5), Mes] resulted in the isolation of the rhenium(III) acetate complex [(DAAm)Re(O(2)CCH(3))(CO)] (3). The mechanistic details of this reaction were explored experimentally. The novel oxorhenium(V) acyl intermediate [(DAAm)Re(O)(C(O)CH(3))] (2) was isolated, and its reactivity with CO was investigated. An unprecedented mechanism is proposed: CO is activated by the metal oxo complex 1 and inserted into the rhenium-methyl bond to yield acyl complex 2, after which subsequent migration of the acyl ligand to the metal oxo ligand yields acetate complex 3. X-ray crystal structures of 2 and 3 are reported.
authors.affiliation: Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, North Carolina 27695-8204, United States.
authors.forename: Jessica L
authors.initials: JL
authors.lastname: Smeltz
authors.forename: Paul D
authors.initials: PD
authors.lastname: Boyle
authors.forename: Elon A
authors.initials: EA
authors.lastname: Ison