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Oxidation of methane by an N-bridged high-valent diiron-oxo species: electronic structure implications on the reactivity

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Title Oxidation of methane by an N-bridged high-valent diiron-oxo species: electronic structure implications on the reactivity
 
Creator ANSARI, M
VYAS, N
ANSARI, A
RAJARAMAN, G
 
Subject IRON BISPIDINE COMPLEXES
RAY CRYSTAL-STRUCTURE
C-H ACTIVATION
EFFECTIVE CORE POTENTIALS
TRANSITION-METAL DIMERS
GAUSSIAN-BASIS SETS
REBOUND MECHANISM
MOLECULAR CALCULATIONS
PHTHALOCYANINE DIMER
ALKANE HYDROXYLATION
 
Description High-valent iron-oxo species are key intermediates in C-H bond activation of several substrates including alkanes. The biomimic heme and non-heme mononuclear Fe(IV)=O complexes are very popular in this area and have been thoroughly studied over the years. These species despite possessing aggressive catalytic ability, cannot easily activate inert C-H bonds such as those of methane. In this context dinuclear complexes have gained attention, particularly mu-nitrido dinuclear iron species [(TPP)(m-CBA)Fe(IV)(mu-N)Fe(IV)-(O)(TPP center dot+)](-) reported lately exhibits remarkable catalytic abilities towards substrates such as methane. Here using DFT methods, we have explored the electronic structure and complex spin-state energetics present in this species. To gain insights into the nature of bonding, we have computed the absorption, the EPR and the Mossbauer parameters and have probed the mechanism of methane oxidation by the dinuclear Fe(IV)=O species. Calculated results are in agreement with the experimental data and our calculations predict that in [(TPP)(m-CBA)Fe(IV)(mu-N)Fe(IV)(O)(TPP center dot+)]-species, the two high-spin iron centres are anti-ferromagnetically coupled leading to a doublet ground state. Our calculations estimate an extremely low kinetic barrier of 26.6 kJ mol(-1) (at doublet surface) for the C-H bond activation of methane by the dinuclear Fe(IV)=O species. Besides these mechanistic studies on the methane activation reveal the unique electronic cooperativity present in this type of dinuclear complex and unravel the key question of why mononuclear analogues are unable to perform such reactions.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2016-01-15T07:08:20Z
2016-01-15T07:08:20Z
2015
 
Type Article
 
Identifier DALTON TRANSACTIONS, 44(34)15232-15243
1477-9226
1477-9234
http://dx.doi.org/10.1039/c5dt01060h
http://dspace.library.iitb.ac.in/jspui/handle/100/18011
 
Language en