title: A delicate electronic balance between metal and ligand in [Cu-P-Cu-P] diamondoids: oxidation state dependent plasticity and the formation of a singlet diradicaloid.
abstract: 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 ( approximately 0.6 A 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.
authors.affiliation: Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
authors.forename: Young Min
authors.initials: YM
authors.lastname: Rhee
authors.forename: Martin
authors.initials: M
authors.lastname: Head-Gordon
mesh_terms: D003300:Copper / Q000737:chemistry*; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D008024:Ligands; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010758:Phosphorus / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D005609:Free Radicals; D008024:Ligands; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D010758:Phosphorus; D003300:Copper