1,4-diaminophthalazine complexes of Re(CO)3

Abstract

1,3-Diiminoisoindolines and substituted variants react with hydrazine to produce 1,4-diaminophthalazines. In this paper, we present the chemistry of 1,4-diaminophthalazine and two modified versions with the Re(CO)3 unit. The 1,4-diaminophthalazine ligand forms a bimetallic complex similar to that seen with unmodified phthalazine. In contrast, the semihemiporphyrazine-derived chelating ligands bind Re(CO)3 as neutral bidentate compounds; the freebase pyrazole and indazole modified 1,4-diaminophthalazines exhibit multiple tautomerization states with ionizable protons. Notably, protonation of the meso bridging nitrogen atom reduces the degree of conjugation between the two halves of the chelate, resulting in a diimine-like complex that lacks significant absorption in the visible spectrum due to the abrogation of the low energy metal to ligand charge transfer (MLCT) transition.