On the Chemistry of Gallium, V. Cyclic Compounds of Gallium and Indium with the 2,2‐Dimethyl‐1,3‐bis‐[(trimethylsilyl)amino]propane Ligand

Reaction of 2,2‐Dimethyl‐N‐lithio‐1,3‐bis[(trimethylsilyl)amino]propane (4a) with RGaBr2 (R = Br, Mes) allows the isolation of the cyclic monomeric amine(amino)gallanes 5 and 6. The cyclic bis(amino) gallanes 7 and 9 as well as the indium homologue 10 were obtained by reaction of gallium halides RGaCl2 (R = Cl, Mes) or InCl3 with dilithiated 4. In the case of R = Mes the product is a monomer. In addition, the tetrakis(amino)gallate 8 was isolated. Single‐crystal X‐ray diffraction studies confirmed the constitutions. Compound 5 has one short GaN single bond (184 pm) and a longer GaN dative bond (204 pm). Compound 7 exhibits a central asymmetrical four‐membered Ga2N2 ring [d(GaN) = 199.4, 205.6 pm] with syn‐oriented substituents. The terminal GaN bond length is 184.3 pm. Two nitrogen atoms bridge the lithium and gallium atom in the gallate 8 [d(LiN) = 206 pm]. Two Li‐H contacts complete the coordination sphere at the lithium atom.