Probing the leaching of carbene-functionalized Ni nanoparticles using a combined HERDF-XAS and DFT-level molecular dynamics approach

Traditionally, Ni-carbene catalysts are regarded as either heterogeneous (functionalized nanoparticles) or homogeneous (complexes). However, in the past decade, seminal work by Ananikov and co-workers has established that Pd- and Pt-based carbene-functionalized nanoparticles, clusters and complexes co-exist in a dynamic equilibrium. High-resolution X-ray absorption measurements (HERFD-XAS) have proven useful for the resolution of complex reaction mixtures. The interpretation of XAS is facilitated using cross-reading based on computational models. Since solvent effects are crucial for these systems, molecular dynamics simulations at the DFT level (DFT-MD) of fully solvated Ni nanoparticles in a solvent cell are expected to provide an appropriate model for these complex systems. We will use a combined HERFD-XAS and DFT-MD approach to probe ligand effects on the behavior of carbene-ligated Ni nanoparticles, focusing on the leaching to clusters and molecular complexes in solution.