Synthesis and Characterization of Iron-Amide and Iron-Imide-Sulfide Clusters
| dc.contributor.author | Zhang, Wei | |
| dc.date.accessioned | 2011-08-30T19:53:10Z | |
| dc.date.available | 2011-08-30T19:53:10Z | |
| dc.date.issued | 2011-08-30T19:53:10Z | |
| dc.date.submitted | 2011 | |
| dc.description.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. | en |
| dc.identifier.uri | http://hdl.handle.net/10012/6189 | |
| dc.language.iso | en | en |
| dc.pending | false | en |
| dc.publisher | University of Waterloo | en |
| dc.subject | Iron-amide clusters | en |
| dc.subject | Iron-imide-sulfide clusters | en |
| dc.subject.program | Chemistry | en |
| dc.title | Synthesis and Characterization of Iron-Amide and Iron-Imide-Sulfide Clusters | en |
| dc.type | Master Thesis | en |
| uws-etd.degree | Master of Science | en |
| uws-etd.degree.department | Chemistry | en |
| uws.peerReviewStatus | Unreviewed | en |
| uws.scholarLevel | Graduate | en |
| uws.typeOfResource | Text | en |