Synthesis, Characterization, and Reactivity of "Reverse Pyridine" Bis(phosphinite) Pincer Complexes

Author: Swisher, Nicholas Adam

Year: 2019

Degree: Dissertation (Ph.D.)

Advisor: Grubbs, Robert H.

Committee Members: Dougherty, Dennis A.; Gray, Harry B.; Peters, Jonas C.; Grubbs, Robert H.

Option: Chemistry

DOI: 10.7907/S8YH-QR85

Abstract

In chapter 1 the synthesis of several pincer complexes based on a "reverse pyridine" bis(phosphinite) ligand motif is described. Coordination of a borane Lewis acid to the parent ligand is described, as well as factors influencing the subsequent metalation of both the "free base" ligand and borane-adduct ligand. The effect of Lewis acid coordination on the spectroscopic and electrochemical properties of the resulting metal complexes is discussed. The reversibility of Lewis acid binding for some complexes is also described.

In chapter 2, an unusual method for carbon-oxygen and carbon-sulfur bond cleavage mediated by alkoxide salts and using silanes as reductants is described.

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