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Published on: November 27, 2015
Beyond Oxides: Nitride as a Ligand in a Neutral IrIX NO3 Molecule Bearing a Transition Metal at High Oxidation State
Łukasz Wolański1, Mateusz Domański1,2, Wojciech Grochala1
1Centre of New Technologies, University of Warsaw, S. Banacha 2c, 02-097, Warsaw, Poland.
Abstract:
Theoretical calculations utilizing relativistic ZORA Hamiltonian point to the conceivable existence of an IrNO3 molecule in C3v geometry. This minimum is shown to correspond to genuine nonavalent iridium nitride trioxide, which is a neutral analogue of cationic [IrO4 ]+ species detected recently. Despite the presence of nitride anion, the molecule is protected by substantial barriers exceeding 200 kJ mol-1 against transformations leading, for example, to global minimum (O=)2 Ir-NO, which contains metal at a lower formal oxidation state.
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