Large pi-systems containing W–N=N–W groups

The compound Cl–W(Mes)3–N=N–W(Mes)3–Cl can polymerize, giving large inorganic pi systems containing N2 and W(Mes)3, where Mes = mesityl. Some of these compounds have been studied in the present paper using B3LYP functional. A description of the molecular orbitals from the pi system is given, explaining the role of the mesityl groups, the terminal chlorines, and the d atomic orbitals from W in the whole conjugated system. Other data such as bond order, atomic partial charges, or geometry are studied. These compounds are also compared with some hypothetical derivatives.