title: Octahedral bipyridine and bipyrimidine dioxomolybdenum(VI) complexes: characterization, application in catalytic epoxidation, and density functional mechanistic study.
abstract: Complexes of the general formula [MoO(2)X(2)L(2)] (X=Cl, Br, Me; L(2)=bipy, bpym) have been prepared and fully characterized, including X-ray crystallographic investigations of all six compounds. Additionally, the highly soluble complex [MoO(2)Cl(2)(4,4'-bis(hexyl)-2,2'-bipyridine)] has been synthesized. The reaction of the complexes with tert-butyl hydroperoxide (TBHP) is an equilibrium reaction, and leads to MoV(I) eta(1)-alkylperoxo complexes that selectively catalyze the epoxidation of olefins. Neither the Mo-X bonds nor the Mo-N bonds are cleaved during this reaction. These experimental results are supported by theoretical calculations, which show that the attack of TBHP at the Mo center through the X-O-N face is energetically favored and the TBHP hydrogen atom is transferred to a terminal oxygen of the Mo=O moiety. After the attack of the olefin on the Mo-bound peroxo oxygen atom, epoxide and tert-butyl alcohol are formed. The latter compound acts as a competitive inhibitor for the TBHP attack, and leads to a significant reduction in the catalytic activity with increasing reaction time.
authors.affiliation: Anorganisch-chemisches Institut der Technischen, Universität München, Lichtenbergstr. 4, 85747 Garching b. München, Germany. fritz.kuehn@ch.tum.de
authors.forename: Fritz E
authors.initials: FE
authors.lastname: Kühn
authors.forename: Michelle
authors.initials: M
authors.lastname: Groarke
authors.forename: Eva
authors.initials: E
authors.lastname: Bencze
authors.forename: Eberhardt
authors.initials: E
authors.lastname: Herdtweck
authors.forename: Angela
authors.initials: A
authors.lastname: Prazeres
authors.forename: Ana M
authors.initials: AM
authors.lastname: Santos
authors.forename: Maria J
authors.initials: MJ
authors.lastname: Calhorda
authors.forename: Carlos C
authors.initials: CC
authors.lastname: Romão
authors.forename: Isabel S
authors.initials: IS
authors.lastname: Gonçalves
authors.forename: André D
authors.initials: AD
authors.lastname: Lopes
authors.forename: Martyn
authors.initials: M
authors.lastname: Pillinger