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.