The monoanion of 2,6-bis(phenylamino)pyridine (HBPAP(-)) has been found to support quadruply bonded Cr-2(4+) and Mo-2(4+) units in Cr-2(HBPAP)(4) (1) and Mo-2(HBPAP)(4) (2). The corresponding dianion BPAP(2-) was able to stabilize the trinuclear complexes, (TBA)(2)Cr-3(BPAP)(4) (3) and (TBA)(2)Ni-3(BPAP)(4) (4), where TBA is the tetrabutylammonium cation. The dinuclear complexes have the typical paddlewheel configuration with Cr-Cr distances of about 1.87 Angstrom and a Mo-Mo distance of 2.0813(5) Angstrom and exhibit a high-field displacement of the corresponding N-H signals caused by the magnetic anisotropy of the quadruple bonds. For the trinuclear complexes, 3 has a linear chain of three chromium atoms arranged in an unsymmetrical fashion with two chromium atoms paired to give a quadruply bonded unit (Cr-Cr distance: 1.904(3) Angstrom) and an isolated, square planar Cr-II unit at 2.589(3) Angstrom from the dimetal unit. On the other hand, the three nickel atoms in 4 are evenly spaced, having Ni...Ni distances of 2.3682(8) Angstrom. The trinuclear compounds show a twisted conformation with an overall torsion angle of about 30 degrees.