|
UWSpace >
University of Waterloo >
Electronic Theses and Dissertations (UW) >
Please use this identifier to cite or link to this item:
http://hdl.handle.net/10012/6189
|
| Title: | Synthesis and Characterization of Iron-Amide and Iron-Imide-Sulfide Clusters |
| Authors: | Zhang, Wei |
| Keywords: | Iron-amide clusters
Iron-imide-sulfide clusters |
| Approved Date: | 30-Aug-2011 |
| Date Submitted: | 2011 |
| Abstract: | The iron-molybdenum cofactor (FeMo cofactor) is the catalytic center of nitrogen fixation in molybdenum-dependent nitrognease enzymes. The resting state cofactor is a complex [MoFe7S9X] cluster, in which the central ligand X is a central hexacoordinated monoatomic light atom (2p), and the exact identity of X is uncertain. The heteroligated, nitrogen-containing core environment of the cofactor cluster may also be relevant to active states, as several mechanistic proposals for cofactor catalysis incorporate substrate-derived nitrogenous moeities into the cluster core during turnover. To this end, we have explored synthetic pathways to the dinuclear and tetranuclear nitrogen-containing iron-sufur clusters, which may mimic the heteroligated core environment of the cofactor. Dinuclear iron-amide clusters Fe2(μ-NHtBu)2[N(SiMe3)2]2 (46) and Fe2(μ-NHtBu)2(μ-S)[N(SiMe3)2]2 (47) are useful precursors for the preparation of [Fe4(NtBu)n(S)4-nCl4]z cubane complexes that span all mixed imide/sulfide core compositions between the classic [Fe4S4] and the more recently reported [Fe4(NtBu)4] homoleptic motifs. The [Fe4NS3] core of the n = 1 cluster is particularly noteworthy in being essentially isometric with the analogous [Fe4S3X] subunit of the FeMo cofactor structure. Synthetic compounds are characterized by single crystal X-ray crystallography, cyclic voltammetry, and UV-Vis, 1H NMR spectroscopies. |
| Program: | Chemistry |
| Department: | Chemistry |
| Degree: | Master of Science |
| URI: | http://hdl.handle.net/10012/6189 |
| Appears in Collections: | Electronic Theses and Dissertations (UW)
Faculty of Science Theses and Dissertations
|
This item is protected by original copyright
|
All items in UWSpace are protected by copyright, with all rights reserved.
|
