Dynamics are intricately linked with activity and selectivity when it comes to catalysis,as noted for instance in the enzymatic principles of induced fit and allostery,and yet the range of motions heterogeneous cataly...Dynamics are intricately linked with activity and selectivity when it comes to catalysis,as noted for instance in the enzymatic principles of induced fit and allostery,and yet the range of motions heterogeneous catalytic sites are able to undergo is poorly understood.Solid-state nuclear magnetic resonance(NMR)spectroscopy is perhaps the only tool capable of probing the rapid conformational dynamics found in heterogeneous catalysts but has historically been restricted by its low sensitivity,limiting the detail with which structures can be resolved.Here,we apply solid-state NMR and dynamic nuclear polarization,in combination with density functional theory modeling,to reveal the high-resolution structure and motional freedom of a scandium supported complex in three dimensions.The results are contrasted with the study of the analogous homoleptic complex in the crystalline state,highlighting the impacts that surface structure may have on the dynamics of supported complexes.展开更多
基金supported by the U.S.Department of Energy(DOE),Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and Biosciences through a DOE Early Career Project(FAP and ALP).Molecular dynamics calculations(DJL)were supported by the Ames Laboratory Chemical Physics program and synthesis(ADS and UK)by the Ames Laboratory Catalysis program.Ames Laboratory is operated for the DOE by Iowa State University under Contract No.DE-AC02-07CH11358Initial work for FAP was supported by an Ames Laboratory Laboratory-Directed Research and Development(LDRD)program.
文摘Dynamics are intricately linked with activity and selectivity when it comes to catalysis,as noted for instance in the enzymatic principles of induced fit and allostery,and yet the range of motions heterogeneous catalytic sites are able to undergo is poorly understood.Solid-state nuclear magnetic resonance(NMR)spectroscopy is perhaps the only tool capable of probing the rapid conformational dynamics found in heterogeneous catalysts but has historically been restricted by its low sensitivity,limiting the detail with which structures can be resolved.Here,we apply solid-state NMR and dynamic nuclear polarization,in combination with density functional theory modeling,to reveal the high-resolution structure and motional freedom of a scandium supported complex in three dimensions.The results are contrasted with the study of the analogous homoleptic complex in the crystalline state,highlighting the impacts that surface structure may have on the dynamics of supported complexes.
