Journal
INORGANICA CHIMICA ACTA
Volume 418, Issue -, Pages 42-50Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2014.04.018
Keywords
DFT; Dinitrosyl; Non-heme iron; Nitric oxide; Broken-symmetry; CASSCF
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Funding
- Russian Foundation for Basic Research [11-03-00132a]
- Romanian Ministry of Education and Research [PCCE 488/2012]
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Dinitrosyl iron complexes have earned attention due to their applications as nitric oxide donors as well as their interesting electronic structures. Typical Fe-NO electromerism issues are complicated in this case by the presence of a second nitrosyl ligand. Each of the formal oxidation states of iron in such complexes - from Fe(III) to Fe(0) - have been shown to be subject to electromerism. Here, broken-symmetry density functional theory data are shown, that reveal asymmetry within iron dithiolate dinitrosyl models in several formal oxidation states. CASSCF calculations on selected models confirm the multiconfigurational character of the Fe(NO)(2) moiety, with the largest contributor at only 44% of the total weight of the wave function. This asymmetry is most noticeable in the excited states; it is further enhanced by solvation and reveals itself even in the ground state in dynamics calculations as well as in reaction pathways connecting the dinitrosyl state to a putative hyponitrite adduct. (C) 2014 Elsevier B. V. All rights reserved.
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