Nitrogen-rich ligands for green transformations involving hydrogen transfer catalysis [electronic resource]

9781109209808

2009

1 online resource (113 p.)

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This dissertation concerns the synthesis and properties of NHC (N-heterocyclic carbene) and terpyridine (terpy) ligands, synthesis of their respective metal complexes and application to hydrogen transfer catalysis. Chapter two describes the synthesis of iridium complexes of triazolium NHCs via silver transmetallation and their application to imine hydrogenation and one-pot reductive amination of alcohols and amines using K2CO 3 as a base. Phosphine analogs of the iridium complexes were found to be better catalysts than their pyridine analogs. Chapter three describes the synthesis of iridium complexes of chelating imidazolium NHCs via silver transmetallation and their application to alcohol activation. N-alkylation of amines with alcohols was achieved using NaHCO3 as a base. Chapter four describes the mechanism of homogeneous iridium-catalyzed alkylation of amines with alcohols from an experimental/computational perspective. Dissociation of amines from the metal complex was found to be the rate determining step both computationally and experimentally. Chapter five describes the application of terpyridine Ru/Ir complexes to beta-alkylation of secondary alcohols with primary alcohols. beta-alkylation of secondary alcohols could be conducted in air and the catalysts were found to be reusable. Chapter six describes the use of terpyRu(PPh3)Cl 2 as an efficient catalyst for converting aldehydes into amides in a one-pot process using NaHCO3 as a base.

Books / Online / Dissertations & Theses

English

July 12, 2011

Thesis (Ph.D.)--Yale University, 2009.

Yale University.