The synthesis and characterisation of several sodium zincate complexes are reported. The all-alkyl monomeric sodium zincate, (PMEDTA)·Na(μ-CH2SiMe3)Zn(t)Bu22, is prepared by combining equimolar quantities of (t)Bu2Zn, (n)BuNa and PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine)]. A similar approach was used to prepare and isolate the unusual dimeric zincate [(PMEDTA)·Na(μ-(n)Bu)Zn(t)Bu2]23. When an equimolar mixture of (n)BuNa, (t)Bu2Zn and TMP(H) (2,2,6,6-tetramethylpiperidine) is combined in hexane, the hetero-tri-leptic TMP(H)-solvated zincate (TMPH)Na(μ-TMP)(μ-(n)Bu)Zn(t)Bu 4 results. Complex 4 can also be prepared using a rational approach [i.e., utilising two molar equivalents of TMP(H)]. When TMEDA is reacted with an equimolar mixture of (n)BuNa, (t)Bu2Zn and TMP(H), the monomeric sodium zincate (TMEDA)Na(μ-TMP)(μ-(n)Bu)Zn(t)Bu 5 was obtained - this complex is structurally similar to the synthetically useful relation (TMEDA)·Na(μ-TMP)(μ-(t)Bu)Zn((t)Bu) 1. By changing the sodium reagent used in the synthesis of 5, it was possible to prepare (TMEDA)Na(μ-TMP)(μ-Me3SiCH2)Zn(t)Bu 6. By reacting 5 with cis-DMP(H) (cis-2,6-dimethylpiperidine), the zincate could thermodynamically function as an amide base, to give the transamination product (TMEDA)Na(μ-cis-DMP)(μ-(n)Bu)Zn(t)Bu 7, although no crystals could be grown. However, when HMDS(H) (1,1,1,3,3,3-hexamethyldisilazane) or PEA(H) [(+)-bis[(R)-1-phenylethyl]amine] is reacted with 5, crystalline (TMEDA)Na(μ-HMDS)(μ-(n)Bu)Zn(t)Bu 8 or (TMEDA)Na(μ-PEA)(μ-(n)Bu)Zn(t)Bu 9 is isolated respectively. With PNA(H) (N-phenylnaphthalen-1-amine) the reaction took a different course and resulted in the formation of the dimeric sodium amide complex [(TMEDA)Na(PNA)]210. When reacted with benzene, it appears that a TMEDA-free variant of 5 functions thermodynamically as an (n)Bu base to yield the previously reported (TMEDA)Na(μ-TMP)((t)Bu)Zn(μ-C6H4)Zn((t)Bu)(μ-TMP)Na(TMEDA) 11. Finally when reacted with TEMPO (2,2,6,6-tetramethylpiperidinyloxy), 5 undergoes a single electron transfer reaction to form (TMEDA)Na(μ-TMP)(μ-TEMPO)Zn(n)Bu 12.