A tridentate diphenolate phosphine ligand H2[OPO] (bis(3,5-di-tert-butyl-2-hydroxyphenyl)phenylphosphine) has been synthesized in high yield. Treatment of H2[OPO] with Ti(OEt)4 in toluene at room temperature produced reddish orange crystalline Ti[OPO]2. The bis-ligand complex Ti[OPO]2 also be obtained from the in situ lithiation of H2[OPO] in THF or toluene followed by addition of TiCl4(THF)2. The reactions of MCl2[N(SiMe3)2]2 (M = Zr, Hf) with H2[OPO] in pentane at room temperature generated cleanly [OPO]2Zr(H2O) and [OPO]2Hf(H2O), respectively, in high yield. Treatment of TiCl4(THF)2 with Ti[OPO]2 in toluene afforded [OPO]TiCl2(THF). The solution and solid-state structures of Ti[OPO]2, [OPO]TiCl2(THF), [OPO]2Zr(H2O) and [OPO]2Hf(H2O) were studied by multinuclear NMR spectroscopy and X-ray crystallography. lithiation of H2[OPO] with n-BuLi in DME solution afforded [OPO]Li2(DME)2. The metathetical reactions of H2[OPO] with NaH or KH in DME solutions, respectively, produced the corresponding complexes [OPO]Na2(DME)2 and {[OPO]K2(DME)2}2. Both [OPO]Li2(DME)2 and [OPO]Na2(DME)2 are highly active catalysts for ring-opening polymerization of caprolactone. A series of tetravalent tin complexes [OPO]SnX2 (X = Cl, Me, n-Bu) also be obtained from the in situ lithiation of H2[OPO] in THF followed by addition of SnCl2X2. A divalent tin complexe [OPO]Sn also be obtained by analogous way from the in situ lithiation of H2[OPO] in pentane followed by addition of SnCl2.
Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0912106-013745 |
Date | 12 September 2006 |
Creators | Chang, Yu-Ning |
Contributors | Liang-Shiu Lee, Lan-Chang Liang, Yen-Nan Chiang, Tsu-Hsin Chang, Teng-Yuan Dong |
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-0912106-013745 |
Rights | not_available, Copyright information available at source archive |
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