Item Details

abstract

Over the past decade, homogeneous gold(I) catalysis has emerged as an important synthetic tool for organic chemists, allowing for the selective activation and subsequent transformation of a wide array of C–C π-systems at low to moderate temperatures15-17. Rapid catalyst deactivation and/or decomposition has been noted as one of the major drawbacks of using these costly species in organic synthesis1, and gaining a mechanistic understanding of how and why gold(I) facilitates these competing processes is thus critical to the future design of novel gold(I) catalytic species geared at specific substrates. Some of our recent work has focused on exploring the effects of ligands’ steric and electronic properties on these processes. To this end, we have prepared and characterized (single-crystal XRD, NMR spectroscopy) a series of novel sterically demanding R-bis(o-biphenyl)phosphine ligands (where R = OPh, t-Bu, Ph), and their corresponding catalytically active gold(I) species. The structure-reactivity relationship of these compounds was assessed by examining their relative rates of intermolecular alkene exchange by dynamic NMR spectroscopy, as well as by their observed deactivation and/or decomposition behavior in solution. This work represents an important advance to the field, as complexes with multiple aryl and/or hydroxyaryl substituents are typically too unstable to allow for full characterization.

subject

catalysis

complex

gold(I)

ligand effects

mechanism

contributor

Griebel, Carolin (author)

Colyer, Christa L (committee chair)

Geyer, Scott M (committee member)

Lukesh, John C (committee member)

date

2019-05-24T08:35:48Z (accessioned)

2021-05-23T08:30:13Z (available)

2019 (issued)

degree

Chemistry (discipline)

embargo

2021-05-23 (terms)

identifier

http://hdl.handle.net/10339/93970 (uri)

language

en (iso)

publisher

Wake Forest University

title

MECHANISTIC IMPLICATIONS OF STERICALLY DEMANDING BIS-(o-BIPHENYL) PHOSPHINE AND PHOSPHINITE LIGANDS IN GOLD(I) CATALYSIS

type

Thesis