The use of the 2,6-diphenoxyphenyl ligand has facilitated the stabilisation of lithium, silane and stannane complexes. The ortho-metallation reaction between 1,3-(PhO)(2)C6H4 and (BuLi)-Bu-n yields 2,6-(PhO)(2)C6H3Li (1); the crystallographically characterised dimer [2,6-(PhO)(2)C6H3Li(OEt2)](2) ([1.Et2O](2)) can be obtained by the crystallisation of 1 from diethyl ether. The reaction between 1 and Me3ECl gives rise to the structurally authenticated complexes 2,6-(PhO)(2)C6H3EMe3 [E = Si, 2; E = Sn, 3]. (C) 2011 Elsevier B.V. All rights reserved.