A Complete Triad of Zero-Valent 17-Electron Monoradicals of Group 7 Elements Stabilized by m-Terphenyl Isocyanides

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 (1), Tc (3), Re (6); ArDArF2 = 2,6-(3,5-(CF3)2C6H3)2­C6H3)) 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 99Tc and 185,187Re 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.