Aluminum complexes, [O3PMe]AlR(R = OtBu, OPh), containing tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)phosphine ([O3P]H3) which is a novel tridentate ligand have been synthesized and characterized by NMR, X-ray diffraction and elemental analysis. Theses complexes were used as catalysts for ring-opening polymerization of £`-caprolactone. We suggested that the stereo effect of catalysts is the main factor in the ring-opening polymerization and compared the mechanism with DFT. In additional, we studied the electronic states and electronic chemistry of [O3PMe]AlR by DFT, UV and PLE.
The novel ligand, bis(3,5-tert-butyl-2-phenoxy) tert-butylphosphine ([tBuOPO]H2), reacted with alkali metals such as n-BuLi, NaH and KH to form a series metal complexes, [tBuOPO]M2(Solvent)x (M = Li, Na, K). These metal complexes are all dimeric molecules characterized by X-ray diffraction, NMR and elemental analysis. Moreover, we reacted {[tBuOPO]Li2(DME)}2 with metal complexes of group 4, TiCl3 and MCl4(THF)2 (M = Ti, Zr, Hf), and we received [tBuOPO]2M and [tBuOPO]MCl2(THF) (M = Ti, Zr, Hf). We also synthesized alkoxide complexes of the series metal complexes and studied the catalytic reactivity for ring-opening polymerizations. Furthermore, tantalum complexes, [tBuOPO]2TaX (X = F, Cl) and [tBuOPO]TaCl3, have been synthesized and characterized. Especially synthesizing [tBuOPO]TaCl3 should be carefully controlled by lowering the concentration of TaCl5.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0713110-200558 |
| Date | 13 July 2010 |
| Creators | Hsu, Yu-lin |
| Contributors | Teng-yuan Dong, Lan-chang Liang, Tsu-hsin Chang |
| 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-0713110-200558 |
| Rights | not_available, Copyright information available at source archive |
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