α-Amidinoazadi(benzopyrro)methenes were synthesized using the Re(CO)3 unit as a templating agent. The products of these template reactions are six-coordinate rhenium complexes, with a facial arrangement of carbonyls, a noncoordinating anion, and a tridentate α-amidinoazadi(benzopyrro)methene ligand. The tridentate ligand shows the conversion of one diiminoisoindoline sp2 carbon to a sp3 carbon, which has been seen in the "helmet" and bicyclic phthalocyanines. The bidentate diiminoisoindoline fragment tilts out of the plane of coordination. Five examples of α-amidinoazadi(benzopyrro)methenes produced from these reactions using different nitrile solvents, including the nitrile activation of acetonitrile, propionitrile, butyronitrile, cyclohexanecarbonitrile, and benzonitrile.