Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and < NH >-transfer to activated olefins

Schlangen M, Neugebauer J, Reiher M, Schroeder D, Lopez JP, Haryono M, Heinemann FW, Grohmann A, Schwarz H (2008)

Publication Status: Published

Publication Type: Journal article

Publication year: 2008

Journal

Journal of the American Chemical Society American Chemical Society

Publisher: AMER CHEMICAL SOC

Book Volume: 130

Pages Range: 4285-4294

Journal Issue: 13

DOI: 10.1021/ja05617w

Abstract

A tetrapodal pentaclentate 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(N(3))]X(2) where X is either Br or PF(6). By means of electrospray ionization mass spectrometry, the dication [(1)Fe(N(3))](2+) can be transferred into the gas phase as an intact entity. Upon collisional activation, [(1)Fe(N(3))](2+) undergoes an expulsion of molecular nitrogen to afford the dicationic nitriclo-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 Clef ins. The precursor clication [(1)Fe(N(3))](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 with CRIS profile

Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Technische Universität Berlin DE Germany (DE) Academy of Sciences of the Czech Republic (ASCR) / Akademie věd České republiky (AVČR) CZ Czech Republic (CZ) Eidgenössische Technische Hochschule Zürich (ETHZ) / Swiss Federal Institute of Technology in Zurich CH Switzerland (CH)

How to cite

APA:

Schlangen, M., Neugebauer, J., Reiher, M., Schroeder, D., Lopez, J.P., Haryono, M.,... Schwarz, H. (2008). Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and < NH >-transfer to activated olefins. Journal of the American Chemical Society, 130(13), 4285-4294. https://doi.org/10.1021/ja05617w

MLA:

Schlangen, Maria, et al. "Gas-phase C-H and N-H bond activation by a high valent nitrido-iron dication and < NH >-transfer to activated olefins." Journal of the American Chemical Society 130.13 (2008): 4285-4294.

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