Metallo-organic complexes are catalytically interesting but difficult to make. Their syntheses often can produce wastes that are particularly toxic. Accurate simulations could streamline the exploratory synthetic efforts, greatly reducing time spent, materials wasted, and production of hazardous wastes. To this end, a family of group 10 metallo-organic complexes are modeled to determine their suitability for catalyzing the formation of carbon-phosphorous bonds.  This suitability depends accessibility of each complex’s metal center, as well as on the availability of reactive electrons; both are evaluated computationally.  Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06-2X analysis predicts a robust planar geometry, regardless of alteration of major components. Both electron density and chemical hardness, however, are impacted by the choice of metal ion and the composition of the monodentate ligand bound to it.  Each of the group 10 diphosphinito complexes studied offer similar overall geometries, but the availability of electrons on the metal—and the anticipated speed of catalyst generation—depends on the final ligand attached to the metal.  Only one monodentate ligand is shown to influence on the energies of the orbitals of the nickel diphosphinito complex sufficiently to make its chemical hardness comparable to that of the more commonly catalytic palladium and platinum analogs.

Predicting catalytic potential: The accessibility and energetics of metal-based electron density for group 10 diphosphinito complexes, interpreted based on density functional theory

251st National Meeting (2016)

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