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Beyond Oxides: Nitride as a Ligand in a Neutral Ir IX NO 3 Molecule Bearing a Transition Metal at High Oxidation State
Author(s) -
Wolański Łukasz,
Domański Mateusz,
Grochala Wojciech,
Szarek Paweł
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902142
Subject(s) - iridium , nitride , molecule , transition metal , metal , oxidation state , cationic polymerization , chemistry , ligand (biochemistry) , crystallography , materials science , inorganic chemistry , polymer chemistry , organic chemistry , biochemistry , receptor , layer (electronics) , catalysis
Theoretical calculations utilizing relativistic ZORA Hamiltonian point to the conceivable existence of an IrNO 3 molecule in C 3 v geometry. This minimum is shown to correspond to genuine nonavalent iridium nitride trioxide, which is a neutral analogue of cationic [IrO 4 ] + 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.