Electron-Rich Nitrido-Bridged Complexes. Structure and Bonding in Triosmium Dinitrido Compounds

Abstract

Triosmium dinitrido-bridged compounds Os 3 (N) 2 Cl 8 L 6 (L = 3-picoline, 4-ethylpyridine, 4- tert -butylpyridine) have been prepared via the thermolysis of the terminal nitrido complexes Os(N)Cl 3 L 2 . 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.