New one-pot methods for the synthesis of metallonium dications [1,2-( 5:σ:σ-C5Me3(CH2)2)( 5-Cp*)Os]2+and [1,1"-( 5:σ-C5Me4CH2)2Os]2+based on decamethylosmocene or its derivatives

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The reaction of Cp*2Os or [Cp*2OsH]+PF6– with oleum on heating or UV photolysis of Cp*2Os in oleum under an inert atmosphere afforded two metallonium dications, viz., [1,2-(η5:σ:σ-C5Me3(CH2)2)(η5-Cp*)Os]2+ and [1,1"-(η5:σ-C5Me4CH2)2Os]2+. The structures of these dications were confirmed by the results of their alkoxylation. The [Os(H)2(Cp*)2]2+ and [Os(H)(Cp*)(C5Me4CH2)]2+ dications were detected as intermediates in the above syntheses. All compounds were characterized by NMR spectroscopy. Calculations of the dications were carried out using the density functional theory (DFT).