Half-Sandwich Titanium(IV) Complexes with Kläui's Tripod Ligand
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- 作者：Tony C. H. Lam ; Eddie Y. Y. Chan ; Wing-Leung Mak ; Samuel M. F. Lo ; Ian D. Williams ; Wing-Tak Wong ; and Wa-Hung Leung
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：March 24, 2003
- 年：2003
- 卷：42
- 期：6
- 页码：1842 - 1847
- 全文大小：161K
- 年卷期：v.42,no.6(March 24, 2003)
- ISSN：1520-510X
文摘
Treatment of [Ti(O-i-Pr)2Cl2] with NaLOEt (LOEt- = [CpCo{P(O)(OEt)2}3]-, Cp = G SRC="/images/gifchars/eta.gif" BORDER=0 >5-C5H5) afforded [LOEtTi(O-i-Pr)2Cl] that reacted with HCl in ether to give [LOEtTiCl3] (1). The average Ti-O and Ti-Cl distances in 1 are 1.975and 2.293 Å, respectively. Reaction of titanyl sulfate with NaLOEt in water followed by addition of HBF4 afforded[LOEtTiF3] (2), the Ti-O and Ti-F distances of which are 2.020(2) and 1.792(2) Å, respectively. The Zr(IV) analogue[LOEtZrF3] (3) was prepared similarly from zirconyl nitrate, NaLOet, and HBF4 in water. The Zr-O and average Zr-Fdistances in 3 are 2.139(2) and 1.938(2) Å, respectively. Treatment of 1 with tetrachlorocatechol (H2Cl4cat) afforded[LOEtTi(Cl4cat)Cl] (4). The average Ti-O(P), Ti-O(C), and Ti-Cl distances in 4 are 1.972, 1.926, and 2.334 Å,respectively. Hydrolysis of 4 in the presence of Et3N yielded the 
ges/entities/mgr.gif">-oxo dimer [(LOEt)2Ti2(Cl4cat)2(ges/entities/mgr.gif">-O)] (5). Theaverage Ti-O(P), Ti-O(C), and Ti-O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) Å. Treatment of 1 with1,1'-binaphthol (BINOLH2) in the presence of Et3N afforded [(LOEt)2Ti2(ges/entities/mgr.gif">-O)2(ges/entities/mgr.gif">-BINOL)]·2BINOLH2 (6·2BINOLH2).Complex 1 is capable of catalyzing ring opening of epoxides with Me3SiN3 under solvent-free conditions presumablyvia a Ti-azide intermediate.