Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and NH-transfer to activated olefins.
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.
Schlangen
Maria
M
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Neugebauer
Johannes
J
Reiher
Markus
M
Schröder
Detlef
D
López
Jesús Pitarch
JP
Haryono
Marco
M
Heinemann
Frank W
FW
Grohmann
Andreas
A
Schwarz
Helmut
H