Synthesis and characterization of a series of rubidium alkoxides and rubidium-titanium double alkoxides

This report investigates the structural aspects of the products isolated from the reactions of a series of titanium alkoxides [[Ti(OR)4]n n = 2, OR = OCH2C(CH3)3 (ONep) (1); n = 1, OC6H3(CH3)2-2,6 (DMP) (2)] with rubidium alkoxides [[Rb(OR)]infinity where OR = (ONep) (3), (DMP) (4), and OC6H3(CH(CH3)2)2-2,6 (DIP) (5)]. The resultant double alkoxides were determined by single crystal X-ray diffraction to be [Rb(mu-ONep)4(py)Ti(ONep)]2 (6), [Rb(mu-DMP)Ti(DMP)4]infinity (7), and [Rb(mu-DMP)2(mu-ONep)2Ti(ONep)]infinity (8). Compound 1 is the previously reported dinculear species with trigonal bipyramidal Ti metal centers whereas compound 2 is a monomer with a tetrahedral Ti center. Suitable X-ray quality crystals of 3 were not isolated. Compounds 4 and 5 demonstrate extended polymeric networks with Rb coordination ranging from two to five utilizing terminal mu- and mu3-OR ligands and pi-interactions of neighboring OAr ligands. The double alkoxide 6 revealed a simple tetranuclear structure with mu-ONep acting as the bridge, terminal ONep ligands on the Ti, and one terminal py on the Rb. For 7 and 8, the pi-interaction facilitated the formation of extended polymeric systems. All complexes were further characterized by FT-IR and multinuclear NMR spectroscopy.