Diphosphines are ubiquitous in transition metal catalysis because they possess an incredible range of electronic and structural parameters that can be used to optimize catalyst performance. One such parameter that has been used with great effect is bite angle. Defined as the P-M-P angle (M = metal), bite angle is known to impact catalytic rates by stabilizing transition state geometries, but it is less clear how these changes affect metal-ligand bonding in the ground state structures. Given that such bonding variations may lead to appreciable differences in reactivity, we have been using ligand K-edge X-ray absorption spectroscopy to investigate how structural parameters such as bite angle affect covalency in metal-ligand bonds. In this presentation, I will discuss recent P and Cl K-edge XAS studies aimed at determining how bite angle variations affect M-P and M-Cl covalency in a series of Ni and Pd diphosphine complexes.

Impact of structure on metal-ligand covalency in late transition metal complexes: Do variations in diphosphine bite angle matter?

249th National Meeting (2015)

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