The first examples of 2,2′-bipyrimidine ligands incorporating bulky or chiral substituents have been prepared by nickel(0)-mediated homo-coupling reactions of chloropyrimidines. The 4,4′-di-(tert-butyl) derivative 2 and the chiral derivative 5, with 4,5-fused bornane groups, have been shown to form mononuclear metal complexes in which they coordinate through the less hindered nitrogen donors.