Reaction of 2-mercapto-1-methylimidazole (methimazole) with tris(dimethylamino)borane, B(NMe2)(3), provides the tetrahedral dimethylamine adduct of tris(methimazolyl)borane, [(Me2HN)B(methimazolyl)(3)]. By contrast, imidazole, 2-methylimidazole, 2-chloroimidazole and benzinlidazole provide the homoleptic tetra-azolyl Systems H[B(azolyl)(4)], and the same product is obtained even when a substoichiometric quantity of the heterocyle is employed. The change in reaction outcome is correlated with the variation of basic pK(a) for the heterocycles. A simple acid-base reaction with elimination of HNMe2 is proposed for the reaction with the weakly basic, but more strongly, acidic, methinlazole. However. for the more strongly basic imidazoles. initial coordination of the heterocycle imine nitrogen to the weakly Lewis acidic boron centre in B(NMe2)(3), to form the tetrahedral adduct [(azole)B(NMe2)(3)] is proposed. The greater availability of the NMe2 lone pairs in this species results in increased basicity and a rapid reaction with further heterocycle to provide the observed H[B(azolyl)(4)] products. For 2-nitroimidazole. the low basicity (and increased N-H acidity) results in the formation of [(HNMe2)B(2-nitroimidazolyl)(3)] on reaction with B(NMe2)(3), analogous to the product formed with methimazole. Both [(HNMe2)B(methimazolyl)(3)] and H[B(benzimidazolyl)(4)] have been structurally characterised by single crystal X-ray crystallography. This chemistry has been exploited to provide a new synthesis of borate-centred tripod ligands. whereby N-methylimidazole is used to activate B(NMe2), to reaction with methimazole to form the new ligand [(N-methimidazole)B(methimazolyl)(3)] in good yield and a complex of this ligand with Ru-II has been structurally characterised.