Bimetallic sodium magnesiates have been employed in metal-halogen exchange for the first time. Utilising the racemic phenoxide ligand 5,5´,6,6´-tetramethyl-3,3´-di-tert-butyl-1,1´-biphenyl-2,2´-diol [(rac)-BIPHEN-H 2 ], the dialkyl sodium magnesiates [(rac)-BIPHEN]Na 2 MgBu 2 (TMEDA) 2 3 and [(rac)-BIPHEN]Na 2 MgBu 2 (PMDETA) 2 4 have been synthesised. Both 3 and 4 can be easily prepared through co-complexation of din -butylmagnesium with the sodiated (rac)-BIPHEN precursor which can be prepared in situ in hydrocarbon solvent. Prior to the main investigation, synthesis of the sodiated precursor [BIPHEN] 2 Na 4 (THF) 4 1 was explored in order to better understand the formation of sodium magnesiates utilising the dianionic (rac)-BIPHEN ligand as the parent ligand. In addition, a BIPHEN-rich sodium magnesiate [BIPHEN] 2 Na 2 Mg(THF) 4 2 was prepared and characterised, and its formation was rationalised. Complex 1 and 4 have also been fully characterised in both solid and solution state. In terms of onward reactivity, 3 and 4 have been tested as potential exchange reagents with aryl and heteroaryl iodides to produce aryl and heteroaryl magnesium phenoxides utilising toluene as a non-polar hydrocarbon solvent. Complex 3 reacted smoothly to give a range of aryl and heteroaryl magnesium phenoxides, whilst 4's reactivity is more sluggish.