Spin-state diversity in a series of Co(ii) PNP pincer bromide complexes

We describe the structural and electronic impacts of modifying the bridging atom in a family of Co(ii) pincer complexes with the formula Co(t-Bu)₂P^EPy^EP(t-Bu)₂Br₂ (Py = pyridine, E = CH₂, NH, and O for compounds 1-3, respectively). Structural characterization by single crystal X-ray diffraction indicates that compounds 1 and 3 are 5-coordinate complexes with both bromides bound to the Co(ii) ion, while compound 2 is square planar with one bromide in the outer coordination sphere. The reduction potentials of 1-3, characterized by cyclic voltammetry, are consistent with the increasing electron-withdrawing character of the pincer ligand as the linker (E) between the pyridine and phosphine arms becomes more electronegative. Magnetic property studies of compounds 1 and 2 confirm high- and low-spin behavior, respectively, through a broad temperature range. However, complex 3 features an unusual combination of high spin S = 3/2 Co(ii) and temperature dependent spin-crossover between S = 3/2 and S = 1/2 states. The different magnetic behaviors observed among the three CoBr₂ pincer complexes reflects the importance of small ligand perturbations on overall coordination geometry and resulting spin state properties.