title: Rapid Dihydrogen Cleavage by Persistent Nitroxide Radicals under Frustrated Lewis Pair Conditions.
abstract: Persistent radicals undergo hydrogen atom abstraction reactions with a great variety of substrates, but not with dihydrogen. It has now been found that the TEMPO radical splits dihydrogen under mild conditions in the presence of the strong bulky B(C6 F5 )3 boron Lewis acid. The reaction is thought to proceed by a typical frustrated Lewis pair mechanism with the TEMPO radical acting as the active Lewis base. The reaction was analyzed by DFT, which indicates that no significant spin density on the hydrogen atoms is accumulated along the H2 splitting reaction path.
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelm-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Xin
authors.initials: X
authors.lastname: Tao
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelm-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Gerald
authors.initials: G
authors.lastname: Kehr
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelm-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Xiaowu
authors.initials: X
authors.lastname: Wang
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelm-Universität Münster, Corrensstraße 40, 48149, Münster, Germany.
authors.forename: Constantin G
authors.initials: CG
authors.lastname: Daniliuc
authors.affiliation: Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstraße 4, 53115, Bonn, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelm-Universität Münster, Corrensstraße 40, 48149, Münster, Germany. erker@uni-muenster.de.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Erker
keywords: boron; dihydrogen splitting; frustrated Lewis pair; persistent radical; radical reactions