The first series of alkali dipyrrinato complexes

The first series of alkali dipyrrinato complexes is reported, encompassing lithium, sodium, and potassium salts of meso-unsubstituted and meso-aryl-substituted derivatives. By varying the substituents at the meso position, the intermolecular distance between the two nitrogen atoms and thus the κ 2 -N,N-bidentate bite angle was altered, as confirmed by comparison of crystallographic structures of dipyrrin free-bases in the solid-state. The mode of bonding varies as the ionic radius of the metal ion increases: solid-state structures reveal lithium to be accommodated in the plane of the dipyrrinato unit, whilst sodium is accommodated out of plane. The reactivity of analogous lithium, sodium, and potassium dipyrrinato complexes increases as the ionic radius of the metal ion increases, in keeping with the concept that the complexes tend towards an increasingly ionic nature as the size of the alkali metal increases.