University of Texas at El Paso
Faculty Sponsor's Department(s):
Chemistry and Biochemistry
Expanding Transition Metal Ketimide Complexes to the Group 10 Elements
The electron-donating properties of ketimide ligands, [R2CN]-, are known to stabilize oxidation states in transition metal ions. For example, ketimide complexes of V(IV), Cr(IV), Mn(IV), Fe(IV), and Co(IV) have been synthesized and effectively characterized. Furthermore, the ketimide ligand set can stabilize multiple oxidation states of the same metal. The purpose of this project is to determine whether oxidation states in Pd and Pt complexes can be stabilized by using a ketimide ligand. In this work, we report the synthesis of new group 10 ketimide complexes through addition of Li[NCtBu2] to MCl2(PhCN)2 (M = Pd, Pt) and PtCl2 under an inert atmosphere. The isolated products were characterized by Nuclear Magnetic Resonance (NMR), Infrared (IR) and UV-Vis spectroscopies, and single crystal x-ray diffraction. The addition of two equivalents of Li[NCtBu2] to PdCl2(PhCN)2 produces a unique Pd7 cluster where the metal centers have been reduced. A Pt analogue is currently being isolated, and is expected to also exhibit a reduction at the metal center. We conclude that, while ketimide ligands can stabilize higher oxidation states of transition metal ions, ketimide complexes of the group 10 elements present lower oxidation states at the metal center.