Transition metal atoms often participate in redox reactions as catalytic sites, where ligand groups play an important role in orchestrating catalytic activity, especially in metalloenzymes. A major issue is to understand connections between oxidation state and geometry at the metal center, because geometric reorganization is directly related to reaction rate. In this article, we analyze an intriguing oxidation-induced geometrical change in [Cu-P-Cu-P] ring structures (similar to 0.6 angstrom change in metal-metal distance) using quantum chemical approaches. We find that the Cu-P interactions in the ring of the neutral species consist of four localized P --> Cu dative bonds. Successive oxidations extract electrons predominantly from P atoms on the ring rather than Cu sites. It emerges that as a result, the Cu-P interactions change and also exhibit partial Cu(3d) --> P donation, which causes the large distortion in geometry. We also find that the dication possesses a large degree of diradical character, forming a rare example of an observed species that is a singlet diradicaloid. This hypothesis is supported by our computational results as well as previously reported experimental features.