Interactions Of Ruthenium(Iii) Complexes Bearing Bis(2-Pyridylcarbonyl)Aminate With Cations At The Carbonyl Group

Bis(2-pyridylcarbonyl)aminate (bpca) coordinates to a ruthenium center with three nitrogen atoms of two pyridyl and one aminate group and the biscarbonylaminate moiety ({O-C-N-C-O}(-)) functions as an alternative coordination site. Interactions of the carbonyl groups of bis(2-pyridylcarbonyl)aminato with cations (M-z(+); Li+, Na+, K+, and Mg2+) were investigated using chloridoacetonitrileruthenium(III) complexes in three different charges, [Ru(III)Cl3-nNCCH(3))(n)(bpca)](m) (n = 0, m = -1; [1](-), n = 1, m = 0; [2], n = 2, m = +1; [3](+)). While the interactions of the Ru(III)-bpca moiety with divalent cation, Mg2+, were observed, monovalent cations, Li+ and Na+, interacted with the Ru-bpca moiety in the Ru(III) state or accompanied by one-electron reduction via a metal ion-coupled electron transfer (MCET). The interactions with cations were related to the electronic structure of the Ru(III)-bpca moiety which was influenced by the electrostatic nature of three coexisting ligands, the charge of the complex and the charge density of M-z(+).