화학공학소재연구정보센터
Inorganic Chemistry, Vol.57, No.20, 12671-12682, 2018
Seeking Redox Activity in a Tetrazinyl Pincer Ligand: Installing Zerovalent Cr and Mo
Reaction of the readily reduced pincer ligand bis-tetrazinylpyridine, btzp, with the zerovalent metal source M(CO)(3)(MeCN)(3) yields M(btzp)(2) for M = Cr, Mo. These diamagnetic molecules show intrapincer bond lengths consistent with major charge transfer from metal to ligand, a result which is further supported by X-ray photoelectron spectroscopy. These molecules show up to five reversible outer-sphere electron transfers by cyclic voltammetry. The electronic structure of neutral M(btzp)(2) is analyzed by DFT and CASSCF calculations, which reveal the degree of back-donation from the metal into pincer pi* orbitals and also subtle differences in metal-ligand interaction for Mo vs Cr. Near-IR absorptions exhibited by both M(btzp)(2) species originate from charge transfer among differently reduced tetrazine rings, which thus further support pincer reduction in these species.