title: Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and NH-transfer to activated olefins.
abstract: A tetrapodal pentadentate nitrogen ligand (2,6-bis(1,1-di(aminomethyl)ethyl)pyridine, 1) is used for the synthesis of the azido-iron(III) complex [(1)Fe(N3)]X2 where X is either Br or PF6. By means of electrospray ionization mass spectrometry, the dication [(1)Fe(N3)]2+ can be transferred into the gas phase as an intact entity. Upon collisional activation, [(1)Fe(N3)]2+ undergoes an expulsion of molecular nitrogen to afford the dicationic nitrido-iron species [(1)FeN]2+ as an intermediate, which upon further activation can intramolecularly activate C-H- and N-H bonds of the chelating ligand 1 or can transfer an NH unit in bimolecular reactions with activated olefins. The precursor dication [(1)Fe(N3)]2+, the resulting nitrido species [(1)FeN]2+, and its possible isomers are investigated by mass spectrometric experiments, isotopic labeling, and complementary computational studies using density functional theory.
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.forename: Johannes
authors.initials: J
authors.lastname: Neugebauer
authors.forename: Markus
authors.initials: M
authors.lastname: Reiher
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Jesús Pitarch
authors.initials: JP
authors.lastname: López
authors.forename: Marco
authors.initials: M
authors.lastname: Haryono
authors.forename: Frank W
authors.initials: FW
authors.lastname: Heinemann
authors.forename: Andreas
authors.initials: A
authors.lastname: Grohmann
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz