Gas-Phase C-H and N-H Bond Activation by a High Valent Nitrido-Iron Dication and <NH>-Transfer to Activated Olefins

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• 作者：Maria Schlangen ; Johannes Neugebauer ; Markus Reiher ; Detlef Schr&ouml ; der ; Jesú ; s Pitarch Ló ; pez ; Marco Haryono ; Frank W. Heinemann ; Andreas Grohmann ; Helmut Schwarz
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：April 2, 2008
• 年：2008
• 卷：130
• 期：13
• 页码：4285 - 4294
• 全文大小：192K
• 年卷期：v.130,no.13(April 2, 2008)
• ISSN：1520-5126

文摘

A tetrapodal pentadentate nitrogen ligand (2,6-bis(1,1-di(aminomethyl)ethyl)pyridine, 1) is usedfor the synthesis of the azido-iron(III) complex [(1)Fe(N₃)]X₂ where X is either Br or PF₆. By means ofelectrospray ionization mass spectrometry, the dication [(1)Fe(N₃)]²⁺ can be transferred into the gas phaseas an intact entity. Upon collisional activation, [(1)Fe(N₃)]²⁺ undergoes an expulsion of molecular nitrogento afford the dicationic nitrido-iron species [(1)FeN]²⁺ as an intermediate, which upon further activation canintramolecularly activate C-H- and N-H bonds of the chelating ligand 1 or can transfer an <NH> unit inbimolecular 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.