The reaction of 1-azidoadmantane, Mn(NR)2 (R=[Si(CH3)3]4 and tBuNHLi yields five membered metallacycle complexes consisting of non-innocent ligand �tetrazene� and manganese. Compounds [Mn(AdNNNNAd)(NSi2Me6)2Li2(AdN3)2] (1 ), [Mn(AdNNNNAd)2Li(thf)2]n (2 ) and  [Mn(AdNNNNAd)2] (3 ) have been obtained from the same reactants under slightly different conditions. Upon delithiation, compound 2  yields compound 3,  whereas compound 1  is isolated by recrystallization of the reaction mixture from pentane. Spectroscopic methods and crystallographic investigations on complexes 1 -3  have determined formal oxidation states of II, III and IV respectively. The electronic structure in redox active tetrazene ligand offered the assignment of oxidation states in Mn centers, and is additionally confirmed by magnetic measurements. The compounds 1 -3  represent the new family of Mn containing tetrazene ligands.  Based on N-N bond lengths, the tetrazene ligand is acting as radicle aionic in 1 -3 .  Cyclic voltammetry studies show a one electron redox couple (IV, III).

Syntheses and characterization of new family of Manganese-tetrazene complexes

248th National Meeting (2014)

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