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Issue 34, 2012
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A computational examination on the structure, spin-state energetics and spectroscopic parameters of high-valent FeIV[double bond, length as m-dash]NTs species

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Abstract

The imidoiron(IV) species are relatively less explored compared to the oxoiron(IV) intermediates. Recently, generation and characterization of a novel imido/oxoiron(IV) species ([(N4Py)FeIV[double bond, length as m-dash]X]2+ X = NTs; 1, O; 2) has been reported with an S = 1 ground state. Although the ground state for 1 and 2 are the same, they are reported to be distinctly different in other aspects. Unlike the oxoiron(IV) species, the Fe(IV) and nitrene combination in 1 lead to eight different spin states. Bearing in mind the complexity arising here, we have undertaken a detailed DFT study on this transient intermediate and probed its electronic structure and bonding in comparison to the oxoiron(IV) unit. Our Molecular Orbital, Energy Decomposition Analysis, and Natural Bond Orbital analysis indicates a weaker σ and non-degenerate π* orbitals for 1 in comparison to a stronger σ and degenerate π* orbitals for 2. The implication of these intricate bonding differences in reactivity is discussed along with the computation of absorption and other spectral parameters. Our results broadly support the proposed S = 1 ground state for 1 and provides some useful insight into its electronic structure.

Graphical abstract: A computational examination on the structure, spin-state energetics and spectroscopic parameters of high-valent FeIV [[double bond, length as m-dash]] NTs species

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Publication details

The article was received on 17 May 2012, accepted on 13 Jun 2012 and first published on 13 Jun 2012


Article type: Paper
DOI: 10.1039/C2DT31071F
Citation: Dalton Trans., 2012,41, 10430-10439
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    A computational examination on the structure, spin-state energetics and spectroscopic parameters of high-valent FeIV[double bond, length as m-dash]NTs species

    M. Jaccob and G. Rajaraman, Dalton Trans., 2012, 41, 10430
    DOI: 10.1039/C2DT31071F

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