How Does Tunneling Contribute to Counterintuitive H-Abstraction Reactivity of Nonheme Fe(IV)O Oxidants with Alkanes?

• Published in: Journal of the American Chemical Society Vol. 137; no. 2; pp. 722 - 733
• Main Authors: Mandal, Debasish, Ramanan, Rajeev, Usharani, Dandamudi, Janardanan, Deepa, Wang, Binju, Shaik, Sason
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 21.01.2015
• Subjects: alkanes; Alkanes - chemistry; ambient temperature; chemical bonding; Hydrogen - chemistry; iron; Iron - chemistry; Kinetics; ligands; Models, Molecular; Molecular Conformation; Oxidants; Oxygen - chemistry; phosphine; prediction; Quantum Theory

This article addresses the intriguing hydrogen-abstraction (H-abstraction) and oxygen-transfer (O-transfer) reactivity of a series of nonheme [FeIV(O)(TMC)(Lax)]z+ complexes, with a tetramethyl cyclam ligand and a variable axial ligand (Lax), toward three substrates: 1,4-cyclohexadiene, 9,10-dihydro...