Synthetic and catalytic studies of Group 11 N-heterocyclic carbene complexes

This thesis presents the synthesis, structure and reactivity of two-coordinate Group 11 metal complexes, supported by N-heterocyclic carbene (NHC) ligands. The NHC ligand was found to stabilize monomeric, terminal fluoride complexes of copper, silver and gold, the last representing the first isolable gold(I) fluoride. These complexes were shown to be reactive synthons for new metal complexes. The ability of the NHC ligand to support unusual coordination environments for these metals inspired us to explore the chemistry of copper(I) bonded to various main group elements, leading to the development of new catalytic reactions. The first well-characterized copper(I) boryl complex was synthesized and shown to react with a variety of unsaturated organic substrates. This complex reacts rapidly with CO2 to form CO and a copper(I) borate complex. The boryl complex may be regenerated by treatment of the borate complex with the bis(pinacolato)diboron, (pin)B-B(pin), giving the stable byproduct (pin)B-O-B(pin). The use of a copper(I) alkoxide precatalyst and stoichiometric diboron reagent results in catalytic reduction of CO2, with high turnover numbers (1000 per Cu) and frequencies (100 per Cu in 1 hour) depending on supporting ligand and reaction conditions.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2006

Author dc:creator

• Laitar, David S. (David Stephen)

Advisor dc:contributor.advisor

• Joseph P. Sadighi.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/36268
• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Identifier URI

http://dspace.mit.edu/handle/1721.1/36268

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/36268