Structural Characterization of Surface Immobilized Platinum Hydrides by Sensitivity-Enhanced 195Pt Solid State NMR Spectroscopy and DFT Calculations

Supported single-site platinum hydride compounds are promising heterogeneous catalysts for organic transformations. Few methods exist to describe the structures of single-site Pt catalysts with atomic resolution because of their disordered structures and low Pt loadings. Here, we study the compounds formed when bis(tri-tert-butylphosphino)platinum, Pt(PtBu3)2, is supported on dehydroxylated SiO2 or SiO2-Al2O3. First, we obtain 1H, 31P and 195Pt ssNMR spectra of four model Pt phosphine compounds with oxidation states of 0 or +2 and coordination numbers between 2 and 4. These compounds are analogs of potential structures present in the supported compounds. 195Pt ssNMR spectra were obtained using 31P{195Pt} sideband selective J-resolved and J-HMQC experiments. The measured 1H and 31P chemical shifts, 31P-195Pt J-couplings and 195Pt CS tensors are shown to be diagnostic of oxidation state and coordination number. Room temperature 1H ssNMR spectra of Pt(PtBu3)2 supported on SiO2 or SiO2-Al2O3 show diagnostic hydride NMR signals, suggesting that Pt(PtBu3)2 undergoes oxidative addition, resulting in surface hydrides and Pt-oxygen bonds to the support surface. MAS dynamic nuclear polarization (DNP) surface-enhanced ssNMR enables 31P{195Pt} correlation NMR experiments on the supported compounds. These experiments enable the measurement of the 31P-195Pt J-coupling constants and 195Pt CS tensors. Combined NMR and DFT analyses suggest that the primary surface platinum species are [HPt(PtBu3)2OSi] on SiO2 and [HPt(PtBu3)2]+[Si-O–-Al] on SiO2-Al2O3. The Pt-oxygen bond length is dependent on the support and estimated as 2.1-2.3 Å and 2.7-3.0 Å for SiO2 and SiO2-Al2O3, respectively.