Heterolytic cleavage of ammonia N–H bond by bifunctional activation in silica-grafted single site Ta(V) imido amido surface complex. Importance of the outer sphere NH3 assistance

• Published in: New journal of chemistry 2011-01, Vol.35 (5), p.1011-1019
• Main Authors: Gouré, Eric, Avenier, Priscilla, Solans-Monfort, Xavier, Veyre, Laurent, Baudouin, Anne, Kaya, Yasemin, Taoufik, Mostafa, Basset, Jean-Marie, Eisenstein, Odile, Quadrelli, Elsje Alessandra
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Coordination chemistry; or physical chemistry; Theoretical and
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/c1nj20032a

Ammonia N-H bond is cleaved at room temperature by the silica-supported tantalum imido amido complex [(≡SiO)2Ta([double bond, length as m-dash]NH)(-NH2)], 2, if excess ammonia is present, but requires 150 °C to achieve the same reaction if only one equivalent NH3 is added to 2. MAS solid-state 15N NMR and in situ IR spectroscopic studies of the reaction of either 15N or 2H labeled ammonia with 2 show that initial coordination of the ammonia is followed by scrambling of either 15N or 2H among ammonia, amido and imido groups. Density functional theory (DFT) calculations with a cluster model [{(μ-O)[(H3SiO)2SiO]2}Ta([double bond, length as m-dash]NH)(-NH2)(NH3)], 2q*NH3, show that the intramolecular H transfer from Ta-NH2 to Ta[double bond, length as m-dash]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.