The late transition metal complexes containing sulfide ligands have trem- endous applications not only in biochemistry but also in industrial catalysis. We have successfully synthesized four different bidentate ligands, 2- (Benzylidene)benzenethiol(NS-1), 2-[2,6-(Dimethylbenzylidene)]benzenethi- ol(NS-2), 2-(2-Chloro-1-methylethylidene)benzenethiol(NS-3) and 2-(Diphe- nylphosphanyl)benzenethiol(PS), and five tridentate ligands, N-{N-[2-(Diph- enylphosphino)benzylidene]-2-sec-butylethylsulfide}(PNS-1), N-{N-[2-(Di- phenylphosphino)benzylamino]-2-sec-butylethylsulfide}(PNS-2), 2-[2-(Diph- enylphosphino)phenylsulfanylmethyl]pyridine(PSN-1), 2-[2-(Diphenylphos- phino)phenylsulfanyl]ethylamine(PSN-2) and 2-(Diphenylphosphino)phenyl- sulfanylacetonitrile(PSN-3). These ligands reacted with the late transition metal (Zn, Ag, Pd, and Ni) salts, and produced complexes 1-12. Besides their spectra, we also obtained crystal structures of complexes 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. We found that the PNS tridentate ligands had different bonding modes in zinc, silver, palladium, and nickel complexes. For examples, in zinc complexes 1 and 2 only P and S atoms were coordinated to the metal while all P, N, and S atoms were coordinated to the Pd metal in Pd complexes. It indicated that thiolether prefers to coordinate to palladium but not to zinc in our cases. When PNS-2 went through different reaction routes, two silver complexes 4 and 5 with different coordination modes a M2L2 type dinuclear complex and a ML2 type mononuclear complex were obtained.. When reacting PNS-2 with nickel, we obtained an unique tetranuclear nickel complex 6. PSN-1 showed two different coordinate modes in complexes 8-10 while PSN-2 and silver produced a dinuclear silver complex 11 that resembled complex 4. PSN-3 coordinated to Pd ion by phosphorus and sulfide atoms. As such, we demonstrated the various coordinated modes in PNS and PSN ligands. Finally PS bidentate ligand reacted with zinc salt produced complex 7 with one oxidized ligand. The variable temperature NMR experiment was also used to probe the structural change that occurred in solution state for 3.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0903103-190835 |
| Date | 03 September 2003 |
| Creators | Huang, Duo-Feng |
| Contributors | Yen-Nan Chiang, none, none, none |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0903103-190835 |
| Rights | unrestricted, Copyright information available at source archive |
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