High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido
Tony Stüker1, Xiya Xia1, Helmut Beckers1
1Institut für Chemie und Biochemie, Anorganische Chemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Abstract:
Pseudo-tetrahedral nitrido trifluorides N≡MF3 (M=Fe, Ru, Os) and square pyramidal nitrido tetrafluorides N≡MF4 (M=Ru, Os) were formed by free-metal-atom reactions with NF3 and subsequently isolated in solid neon at 5 K. Their IR spectra were recorded and analyzed aided by quantum-chemical calculations. For a d2 electron configuration of the N≡MF3 compounds in C3v symmetry, Hund's rule predict a high-spin 3 A2 ground state with two parallel spin electrons and two degenerate metal d(δ)-orbitals. The corresponding high-spin 3 A2 ground state was, however, only found for N≡FeF3 , the first experimentally verified neutral nitrido FeVI species. The valence-isoelectronic N≡RuF3 and N≡OsF3 adopt different angular distorted singlet structures. For N≡RuF3 , the triplet 3 A2 state is only 5 kJ mol-1 higher in energy than the singlet 1 A' ground state, and the magnetically bistable molecular N≡OsF3 with two distorted near degenerate 1 A' and 3 A" electronic states were experimentally detected at 5 K in solid neon.
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