Abstract

The paramagnetic complex [Rh(trop 2dach)] 2 was obtained by reduction of the almost planar 16-electron cationic precursor complex, [Rh(trop 2dach)] + 1 and characterized by EPR spectroscopy [ g 11 = 2.069, g 22 = 2.014, g 33 = 1.964, g iso = 2.016; A(Rh) = (<40, 29, 30)]. The unobservable small nitrogen hyperfine coupling and DFT calculations show that most of the spin density is localized on the hydrocarbon ligand framework and only about 35% on the metal center. DFT calculations on various 17 electron rhodium complexes with carbonyl, olefine, or phosphane ligands like [Rh(CO) 4] , [Rh(cod) 2] , and [Rh(dppe) 2] reveal that in none of these the spin density at the metal center exceeds 45%. That is all formally Rh(0) complexes reported to date are better described as highly delocalized radicals and an assignment of the formal metal oxidation state is not meaningful.

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