Date of Award
Doctor of Philosophy (PhD)
This thesis summarizes synthetic, catalytic, and mechanistic work towards improved understanding of steric and electronic ligand effects in systems supported by the frequently used RPNR’P (RPNR’P = R’N(CH2CH2PR2)2) pincer ligand. Chapter 1 provides an overview of previous work on the synthetic and catalytic effects of varying the substituents of the RPNR’P ligand or other ancillary ligands. Chapter 2 describes the synthesis and catalytic activity of a series of novel iPrPNMeP iron isonitrile complexes to investigate the role of the π-acid ligand. In chapter 3, an active and productive additive-free formic acid dehydrogenation system is developed and optimized using an iron iPrPNMeP catalyst. Chapter 4 discusses the synthesis of a new N-phenyl ligand iPrPNPhP and its coordination to ruthenium, followed by a detailed catalytic and mechanistic comparison between iPrPNR’P ruthenium complexes which differ only in their N-substitution. In chapter 5, the synthesis and characterization of a series of base metal iPrPNPhP complexes is described.
Curley, Julia Bryant, "Ligand Effects on (De)hydrogenative Catalysis using the RPNR’P Pincer Scaffold" (2021). Yale Graduate School of Arts and Sciences Dissertations. 319.