Triosmium dinitrido-bridged compounds Os-3(N)(2)Cl8L6 (L = 3-picoline, 4-ethylpyridine, 4-tert-butylpyridine) have been prepared via the thermolysis of the terminal nitrido complexes Os(N)Cl3L2. X-ray structural studies of Os-3(N)(2)Cl-8(4-Etpy)(6) and Os-3(N)(2)Cl-8(4-t-Bupy)(6) reveal a linear Os-3(N)(2) unit with multiple bonding significantly localized in the outer osmium-nitrogen bonds in Os-V=N-Os-IV-N=Os-V. A Simple model of bonding and electronic structure consistent with the solid-state structures is discussed.