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N,N′-Dialkyl sulfur diimides (1), R(NSN)R [R = Me (a), Et (b),  n Pr (c),  n Bu (d)] react with cyclic bis(amino)stannylenes such as 1,3-di-tert-butyl-4,4-dimethyl-1,3,4,2λ 2 -diazasilastannetedine (2) or 1,3-di-tert-butyl-4,4,5,5-tetramethyl-1,3,4,5,2λ 2 -diazadisilastannolidine (3) in a 2:1 ratio to give the new spiro-tin(IV) compounds 5a-d, 6b and 6c, built from the respective cyclic bis(amino)stannylene and a seven-membered ring in which the two sulfur diimide groups are coupled via a N-N bond and across the tin atom. A 1:1 adduct 4 is proposed as an intermediate which is the final product 4e in the case of R =  t Bu (1e). The products were characterized by multinuclear magnetic resonance ( 1 H,  13 C,  15 N,  29 Si,  119 Sn NMR), and in the case of 5c the molecular structure was determined by single crystal X-ray structure analysis [monoclinic, space group C2/c ; a = 1504.1(3), b = 1393.3(3), c = 1688.6(3) pm; β = 115.71(3)°].

New Spiro-Tin Compounds: Reaction of N,N′-Dialkyl Sulfur Diimides with Cyclic Bis(amino)stannylenes - Unexpected Formation of a N-N Bond