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Bioinorganic - Organometallic  
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DALEY GROUP RESEARCH OVERVIEW

For more information about a project, please view the Daley group members’ individual pages for updates and/or contact Dr. Daley to learn more. If you are interested in joining the Daley Group, please click on this application form, complete it, and return it to Dr. Daley. Please note that Dr. Daley is not accepting any new students during the 2013 - 2014 academic year

Bioinorganic Chemistry
The Daley group is currently investigating systems that contain metal-amidato (M-NC(O))bonds in order to better understand their properties and chemistry.  Metal-amidato bonding is rare in nature but it has been observed in a number of very interesting biological systems such as (1) nitrogenase, (2) carbon monoxide dehydrogenase acetyl coenzyme A: CODH, and (3) nitrile hydratase: NHase. 

Direct Nitrile Hydratase Analogues:  Our research focuses on the development of synthetic analogues of the nitrile hydratase active site.  Currently, we develop 4– and 5-coordinate model ligand systems that more accurately model the structural of the active site in NHase, including the incorporation of thiolate moieties.  We also investigate the physical and chemical properties of their Fe(III) and Co(III) metal complexes in comparison to that of the native NHase.

Indirect Nitrile Hydratase Analogues:  We have recently begun to investigate the nature of metal-amidato bonding in the presence of other bonding moieties by designing and synthesizing ligands inspired by the NHase active site.  We are using a phosphorus-for-sulfur atom exchange (substitution) methodology that has been used successfully to develop systems that often have improved properties over their sulfur-based analogues.  Preliminary studies have begun with group 10 metals (specifically palladium) which are known to form stable neutral 4-coordinate diamidato-bisphosphine complexes.

The Daley group thanks these agencies for current and former support:

The National Science Foundation
Research Corporartion
The Camille & Henry Dreyfus Foundation
American Philosophical Society

NSF       Drefus Foundation    

 

Organometallic Chemistry
The Daley group is also developing a new ligand system for potential use in metal-mediated asymmetric catalysis reactions.  Chiral phosphorus and nitrogen-based ligands are the most commonly used in asymmetric catalysis today.  In the case of the phosphine systems, ligands such as BINAP have been extremely successful.  The Daley group is interested in the nitrogen-based ligands, which have also been highly successful as noted by the extensive use of the ligand PyBox. 

Currently, we are developing a chiral tridentate ligand inspired from the highly successful oxazoline moiety and the robust and interesting isoindoline moiety.  This project is in its infancy, but will be expanded once the desired ligand has been successfully synthesized and characterized.  Once obtained, numerous catalysis studies will then be investigated.

The Daley group thanks these agencies for current and former support:

The ACS Petroleum Research Foundation