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Fluoro Nitrenoid Complexes FN=MF 2 (M=Co, Rh, Ir): Electronic Structure Dichotomy and Formation of Nitrido Fluorides N≡MF 3
Author(s) -
Stüker Tony,
Hohmann Thomas,
Beckers Helmut,
Riedel Sebastian
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010950
Subject(s) - chemistry , nitrene , endothermic process , crystallography , ligand (biochemistry) , metal , infrared spectroscopy , ternary operation , excited state , chemical bond , adduct , adsorption , atomic physics , biochemistry , physics , receptor , organic chemistry , computer science , programming language , catalysis
The fluoronitrenoid metal complexes FNCoF 2 and FNRhF 2 as well as the first ternary Rh VI and Ir VI complexes NIrF 3 and NRhF 3 are described. They were obtained by the reaction of excited Group‐9 metal atoms with NF 3 and their IR spectra, isolated in solid rare gases (neon and argon), were recorded. Aided by the observed 14/15 N 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 FNCoF 2 (1056.8 cm −1 ) and FNRhF 2 (872.6 cm −1 ) are very different and their N−M bonds vary greatly. In FNCoF 2 , the FN ligand is singly bonded to Co and bears considerable iminyl/nitrene radical character, while the N−Rh bond in FNRhF 2 is a strong double bond with comparatively strong σ‐ and π‐bonds. The anticipated rearrangement of FNCoF 2 to the nitrido Co VI complex is predicted to be endothermic and was not observed.