Radical Monocationic Guanidino-Functionalized Aromatic Compounds (GFAs) as Bridging Ligands in Dinuclear Metal Acetate Complexes: Synthesis, Electronic Structure, and Magnetic Coupling

Inorganic Chemistry
Benjamin EberleHans-Jörg Himmel

Abstract

In this work, the oxidation of several new dinuclear metal (M) acetate complexes of the redox-active guanidino-functionalized aromatic compound (GFA) 1,2,4,5-tetrakis(tetramethylguanidino)benzene (1) was studied. The complexes [1{M(OAc)2}2] (M = Ni or Pd) were oxidized to the radical monocationic complexes [1{M(OAc)2}2](+ •). From CV (cyclic voltammetry) measurements, the Gibbs free enthalpy for disproportionation of [1{M(OAc)2}2](+ •) into [1{M(OAc)2}2] and [1{M(OAc)2}2](2+) could be estimated to be roughly +20 kJ mol(-1) in CH2Cl2 solution. A characteristic feature of the [1{M(OAc)2}2](+ •) complexes is the presence of intense metal-ligand charge-transfer bands in the electronic absorption spectra. The complex [1{Ni(OAc)2}2](+ •) combines three paramagnetic centers with four metal-centered unpaired electrons and a ligand centered π-radical and exhibits a sextet electronic ground state. Spin distribution of the Ni complexes was evaluated by paramagnetic (1)H and (13)C NMR and was correlated with calculations. The strong ferromagnetic metal-ligand magnetic coupling was studied in the solid state by magnetometric (SQUID) measurements and by quantum chemical (DFT) calculations. The temperature dependence of the paramagnetic NMR s...Continue Reading

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