Abstract
Ammonia N-H bond is cleaved at room temperature by the silica-supported tantalum imido amido complex [( SiO)(2)Ta(QNH)(-NH2)], 2, if excess ammonia is present, but requires 150 degrees C to achieve the same reaction if only one equivalent NH3 is added to 2. MAS solid-state N-15 NMR and in situ IR spectroscopic studies of the reaction of either N-15 or 2 H labeled ammonia with 2 show that initial coordination of the ammonia is followed by scrambling of either N-15 or 2 H among ammonia, amido and imido groups. Density functional theory (DFT) calculations with a cluster model [{(mu-O)[(H3SiO)(2)SiO](2)} Ta(=NH)(-NH2)(NH3)], 2(q).NH3, show that the intramolecular H transfer from Ta-NH2 to Ta=NH is ruled out, but the H transfers from the coordinated ammonia to the amido and imido groups have accessible energy barriers. The energy barrier for the ammonia N-H activation by the Ta-amido group is energetically preferred relative to the Ta-imido group. The importance of excess NH3 for getting full isotope scrambling is rationalized by an outer sphere assistance of ammonia acting as proton transfer agent, which equalizes the energy barriers for H transfer from coordinated ammonia to the amido and imido groups. In contrast, additional coordinated ammonia does not favor significantly the H transfer. These results rationalize the experimental conditions used.