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Published on: April 19, 2019
A Complete Triad of Zero-Valent 17-Electron Monoradicals of Group 7 Elements Stabilized by m-Terphenyl Isocyanides
Federico Salsi1, Shuai Wang2, Christian Teutloff3
1Institute of Chemistry and Biochemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Abstract:
The first consistent series of mononuclear 17-electron complexes of three Group 7 elements has been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods. The paramagnetic compounds have a composition of [M0 (CO)(CNp-F-ArDArF2 )4 ] (M=Mn, Tc, Re; ArDArF2 =2,6-(3,5-(CF3 )2 C6 H3 )2 C6 H2 F) and are stabilized by four sterically encumbering isocyanides, which prevent the metalloradicals from dimerization. They have a square pyramidal structure with the carbonyl ligands as apexes. The frozen-solution EPR spectra of the rhenium and technetium compounds are clearly anisotropic with large 99 Tc and 185,187 Re hyperfine interactions for one component. High-field EPR (Q band and W band) has been applied for the elucidation of the EPR parameters of the manganese(0) complex.
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