The reaction of an alkali metal precursor, a diol and a dimethylamido reagent E(NMe₂)_n (E = Sn, n = 2; E = As/Sb, n = 3) has produced a wide variety of complexes, most of which are ion-contracted species. A range of heterobimetallic Sn(II)/alkali metal complexes have been synthesised. Complexes [SnBinol₂Li₂(THF)₄] 1 and [SnBinol₂Li₂(HMPA)₄] 2 are monomeric, [Sn(C₁₀H₆O₂)₂Li₂(HMPA)₃]₂ 3 is dimeric, the complexes [Sn(C₁₀H₆O₂)₂Li₂(DMF)₂]_n 4 and [SnBinol₂Na₂(DMF)₄]_n 5 are polymeric whilst [Sn₈(C₆H₄O₂)₁₂K₈(THF)₈]_n 6 has a two dimensional network structure. Complexes 1 - 5 contain the [Sn(RO₂)₂]^2- dianion. The complexes 3 and 4 contain a [O₂Li₂O₂] ladder which forms between the Sn(II) centres whilst complex 5 has a corner sharing diamond structure to the backbone of the polymer. In addition similar reactions have serendipitously produced the Sn(II) complex [{Sn₂(C₆H₄O₂)₃}{H₂NMe₂}₂. THF. ½HNMe₂] 7, the Sn(IV) complex [{Sn^IV(C₆H₄O₂)₃}{H₂NMe₂}₂.HMPA] 8 and the mixed Sn(IV)/alkali metal complexes [Sn^IV(C₁₀H₆O₂)₃][Li(HMPA)₄]₂ 9 and the polymeric [Sn^IV(C₆H₄O₂)₃K₂(THF)₂]_n 10. The complexes 6 and 7 contain the [Sn₂(RO₂)₃]^2- dianion, whilst 8 - 10 incorporate the [Sn^IV (RO₂)₃]^2- dianion in which the Sn centre has been oxidised to Sn(IV). Complexes 7 - 9 are ion-separated structures. The reactions of E(NMe₂)₃ (where E = As/Sb) produced the polymeric [Sb(C₁₀H₆O₂)₃Na₃(THF)₃(DMF)₂]_n 11 and the heterobimetallic complex [As₂(4-^tBuC₆H₃O₂)₉(4-^tBuC₆H₃(O)OH)Li₁₃(THF)₁₀.C₆H₅CH₃] 12. Complex 12 contains the novel [Li₈O₆] cage structure. This cage is also present in complex [{C₆H₅N(CH₂)₂O}₄{C₆H₅NH(CH₂)₂O}₂Li₁₀(THF)₆]. 13. The introduction of water into the As(NMe₂)₃ reactions resulted in the formation of the As oxoanion complexes 14 - 19, where complexes 14 - 17 and 19 contain the [AsO₃] moiety. The complex [As₄(L)₂(HL)₄(H₂L)Li₇O₂.C₆H₅CH₃] 14 (where H₃L = CH₃CH(OH)CH₂NHCH₂CH(OH)CH₃) contains a [Li₆O₅OH] cage. The complexes [As₂Biphenol₂Li₂O₂(TMEDA)₂] 15, [As₂Binol₂Li₂O₂(DMF)₄] 16 [As₂Binol₂Na₂O₂(DMF)₄] 17, are dimeric and display a central planar [AsOM₂OAs] M = Li/Na) moiety. [As₄Binol₄Li₁₂O₈(DMF)₄(HMPA)₄] 18 is unique in that the diol chelates to the alkali metal rather than the p-block metal. Complex [As₁₀Biphenol₁₀K₁₀O₁₀(THF)₄. THF.½C₆H₅CH₃]_n 19 is a polymeric chain with branches that contain [K₄O₄]⁴⁺ tetra-anionic cubane type structures.