Multinuclear Alkali Metal Complexes of a Triphenylene-Based Hexamine and the Transmetalation to Tris(N-heterocyclic tetrylenes) (Ge, Sn, Pb)

A C₃-symmetric hexamine (LH₆) based on the triphenylene and ortho-phenylenediamine (PDAH₂) skeletons has been synthesized, and was partially or fully deprotonated upon treatment with alkali metal agents to afford amino-amido or diamido coordination sites. Four alkali metal complexes, the dinuclear [Na₂(LH₄)(DME)₅] (1) and [K₂(LH₄)(DME)₄] (2), trinuclear [K₃(LH₃)(DME)₆] (3), and hexanuclear [Li₆(L)(DME)₆] (4), were obtained and used in transmetalation/ligand exchange with other metals. The hexalithium salt of the fully deprotonated ligand, [Li₆L], reacted with heavier group 14 element halides to yield three tris(N-heterocyclic tetrylenes), the germylene [Ge₃(L)] (5), stannylene [Sn₃(L)] (6), and plumbylene [Pb₃(L)] (7). The synthesis and crystal and electronic structures of these compounds are reported.