Cycloaddition reactions of distibene [L(Me2N)GaSb]2 (L = HC[C(Me)NDipp]2; Dipp = 2,6-i-Pr2C6H3)[double bond, length as m-dash] with a series of organoazides RN3 (R = Ph, p-CF3Ph, 1-adamantyl (ada)) yielded azadistibiranes [L(Me2N)GaSb]2NR (R = Ph 1, p-CF3Ph 2, ada 3), whereas Me3SiN3 reacted with insertion into one Ga-Sb bond and formation of L(Me2N)GaSbSb(NSiMe3)Ga(NMe2)L (4). Analogous compounds 5 and 6 formed after heating of 1 and 2 above 60 °C. Prolonged heating of 5 resulted in a [2 + 2] cycloaddition accompanied by elimination of LGa(NMe2)2 and formation of tetrastibacyclobutane 7, while the reaction of 5 with a second equivalent of PhN3 gave heteroleptic azadistibirane 9, which isomerized at elevated temperature to distibene 10. Cycloaddition also occurred in reactions of [L(X)GaSb]2 (X = NMe2, OEt, Cl) with Me3Si(H)CN2, yielding distibiranes [L(X)GaSb]2C(H)SiMe3 (X = NMe211, OEt 12, Cl 13). Compounds 1-13 were characterized by IR, UV-Vis and NMR spectroscopy and sc-XRD. The mechanism of the reaction of [L(Me2N)GaSb]2 with PhN3 and Me3SiN3 and the electronic nature of the resulting compounds were studied by DFT calculations.
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