The organohydrazide chelate complexes M-III(NNpy)(PPh3)(2)Cl-2 (1, 3) (M = Re, Tc) have been synthesized using the organohydrazine 2-hydrazinopyridine. The chelated organohydrazide is a diazenido(1-) ligand that forms a five-membered ring with the metal center. An X-ray structural analysis of 1 indicates that there is a delocalized pi-system formed by the chelate ring. These octahedral, d(4) metal complexes have diamagnetic H-1 NMR spectra. Complex 1, C41.50H34Cl2N3O0.5P2Re, crystallizes in the triclinic space group with a = 10.5549(7) Angstrom, b = 12.2699(8) Angstrom, c = 16.8206(12) Angstrom, alpha = 105.9050(10)degrees, beta = 95.8930(10)degrees, gamma = 111.0100(10)degrees, V = 1906.1(2) Angstrom(3), Z = 2, and R = 0.0650 based on 5268 unique reflections. The FABMS+ in (p-nitrobenzyl alcohol) of 3 reveals a parent ion peak at m/z 799.2. The complex [Re(HNNpy)(NNpy)(PMe2Ph)(2)Cl](+)[Cl](-) (2) contains a chelated, neutral organodiazene ligand and a linear, diazenido(1-) ligand. The X-ray structural analysis of 2, C26H30Cl2N6P2Re, indicates a delocalized ct-system formed by the chelate ring. The H-1 NMR spectrum of 2 is not paramagnetically shifted. Complex 2 crystallizes in the orthorhombic space group Pna2(1) with a = 17.383(4) Angstrom, b = 13.967(3) Angstrom, c = 12.002(2) Angstrom, V = 2913.9(10) Angstrom(3), Z = 4, and R = 0.0384 based on 3083 unique reflections.