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- Title
Fluoro Nitrenoid Complexes FN=MF<sub>2</sub> (M=Co, Rh, Ir): Electronic Structure Dichotomy and Formation of Nitrido Fluorides N≡MF<sub>3</sub>.
- Authors
Stüker, Tony; Hohmann, Thomas; Beckers, Helmut; Riedel, Sebastian
- Abstract
The fluoronitrenoid metal complexes FNCoF2 and FNRhF2 as well as the first ternary RhVI and IrVI complexes NIrF3 and NRhF3 are described. They were obtained by the reaction of excited Group‐9 metal atoms with NF3 and their IR spectra, isolated in solid rare gases (neon and argon), were recorded. Aided by the observed 14/15N isotope shifts and quantum‐chemical predictions, all four stretching fundamentals of the novel complexes were safely assigned. The F−N stretching frequencies of the fluoronitrenoid complexes FNCoF2 (1056.8 cm−1) and FNRhF2 (872.6 cm−1) are very different and their N−M bonds vary greatly. In FNCoF2, the FN ligand is singly bonded to Co and bears considerable iminyl/nitrene radical character, while the N−Rh bond in FNRhF2 is a strong double bond with comparatively strong σ‐ and π‐bonds. The anticipated rearrangement of FNCoF2 to the nitrido CoVI complex is predicted to be endothermic and was not observed.
- Subjects
NEON; SOLID rare gases; ELECTRONIC structure; DOUBLE bonds; ISOTOPE shift; FLUORIDES
- Publication
Angewandte Chemie, 2020, Vol 132, Issue 51, p23374
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202010950