UBC Theses and Dissertations
Electronic structure studies of ruthenium-based catalysts for olefin metathesis : an x-ray absoprtion spectroscopy perspective Delgado Jaime, Mario Ulises
Interest in olefin metathesis has increased over the years with the development of ruthenium-based catalysts. Their unique properties have allowed their use in numerous industrial and laboratory processes in relatively mild conditions and in combination with a wide range of solvents. Several studies have provided insights into how these catalysts work, but very little has been done in order to understand why they work that way; an important aspect that has the potential of benefiting chemists while designing new catalysts. The research introduced here has focused on the fundamental understanding of their reactivity by exploring their electronic structure, using a combination of synchrotron-based X-ray-absorption (XAS) techniques in combination with DFT calculations and multiplet simulations. As part of the experimental work, samples from various ruthenium-based catalysts classified as first-generation (whenever the ancillary ligand is a phosphine) or as second-generation analogues (whenever this ligand is an N-heterocyclic carbene, NHC) were used. The Ru K-edge XAS data have revealed that the ruthenium centre in second-generation analogues is more positively charged than the corresponding first-generation counterparts. This offers a rationale for previously observed kinetic results, which have shown a slower initial step for the second-generation Grubbs catalyst. At the same time, they raise questions in a more fundamental level on whether or not NHCs are truly better charge donors than phosphine ligands. DFT results are consistent and the ongoing analyses of the Cl K- and C K-edge XAS data indicate similar overall bonding structures between first- and second- generation analogues. In addition, from preliminary results on these edges, two possible identities of substantially different nature have emerged for the LUMO orbital. In this regard, the final conclusion should provide important insights on through which orbital the metathesis reaction gets started. As a side product, the analyses of the challenging Cl K-edge XAS data have inspired the development of a new methodology and a Matlab-based computer program for fitting. Ultimately, the methods and techniques detailed here can serve as the foundation for the comprehensive study of other related systems relevant to olefin metathesis, or in general, to the field of homogeneous catalysis.
Item Citations and Data
Attribution 3.0 Unported