“…26,58,59,60 This observation is in line with predominantly diphosphenediide-centered oxidation of 2 and an unsymmetric spin density distribution of radical cation 3. 64 DFT calculations confirm this picture and locate the spin density of 3 mainly on the P2 fragment (Figure 2C) as a result of depopulation of the *(P2) HOMO of parent 2. Accordingly, the P-P bond order increases upon oxidation, as reflected by the Wiberg bond orders and the QTAIM delocalization indices (WBI; 2: 1.86, 3: 2.09, and DI(P,P); 2: 1.81, 3: 1.95; Figure S81-S82).…”