Natural Abundance 195Pt-13C Correlation NMR Spectroscopy on Surfaces Enabled by Fast MAS Dynamic Nuclear Polarization

Abstract

Surface organometallic chemistry has developed as an effective strategy for the rational design and synthesis of well-defined, single-site Pt-based heterogeneous catalysts. Given its high sensitivity to changes in electronic structure, 195Pt solid-state NMR spectroscopy offers a unique approach to investigate the chemical structure and local environment of Pt surface sites, providing invaluable insights for establishing structure-activity relationships. However, this approach is typically hindered by severe sensitivity issues, due to the low loading of Pt sites and the often-encountered large 195Pt chemical shift anisotropies. To overcome this limitation, 195Pt NMR signature of surface metal centers can be indirectly detected through protons. Indirect detection on 13C spins, has also been demonstrated to be feasible by combining isotopic labeling with dynamic nuclear polarization (DNP). Here, we extend this methodology to a supported Pt complex at natural abundance. The material was prepared by grafting (COD)PtMeOSi(OtBu)3 (COD = 1,5-cyclooctadiene, Me = methyl and tBu = tert-butyl) onto partially dehydroxylated silica. DNP enhanced two-dimensional through-bond 13C{195Pt} heteronuclear correlation experiments were successfully implemented at fast magic angle spinning. They enabled the detection of the 0.37% NMR-responsive surface species, thereby showcasing the remarkable sensitivity of this approach and its broad applicability. Key bonding information was obtained by measuring the correlated 13C and 195Pt isotopic chemical shifts as well as 1J(13C-195Pt) coupling constants, confirming directly the coordination structure of the surface Pt sites.