A General Pathway for the Synthesis of Gallastibenes containing Ga=Sb Double Bonds

Reactions of three equivalents of LGa {L=HC[C(Me)N(2,6‐iPr2C6H3)]2} with SbX3 (X=F, Cl, Br, I) proceed with insertion into the Sb−X bond, elimination of LGaX2, and formation of LGaSbGa(X)L (X=F 1, Cl 2, Br 3, I 4) containing a Ga=Sb double bond. In contrast, the 2:1 molar ratio reaction of LGa and SbCl3 initially gives the twofold insertion product [L(Cl)Ga]2SbCl 7, which could not be isolated due to its strong tendency toward elimination of LGaCl2 and formation of distibene [L(Cl)GaSb]25 at 25 °C or cyclotristibine [L(Cl)GaSb]36 at 8 °C. The formation of 16 can be rationalized by formation of the Ga‐substituted stibinidene L(X)GaSb as reaction intermediate.

Dedicated to Prof. W. A. Herrmann on the occasion of his 70th birthday.


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