Proximate, "Parallel-In-Plane" Preoriented Bis(diazenes) − In-Plane Delocalized Bis(homoconjugated) 4N/5(6)e Anions

Synthetic details are presented for a series of more or less rigid, “parallel‐in‐plane” preoriented bis(diazenes), with N=N/N=N distances (d) of 3.3−2.9 Å and interorbital angles (ψ) of 142−164° (X‐ray crystal structures). DFT calculations (B3LYP/6−31G*) and one‐/two‐electron reduction experiments with the two least preoriented, most “distant” bis(diazenes) (dN=N/N=N ca. 3.3 Å; ψ 142−146°) provide more insight into the structural prerequisites for bis(homoconjugative) in‐plane electron delocalization in 4N/5e radical anions and 4N/6e dianions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)