Mono(pentamethylcyclopentadienyl)titanium and -zirconium complexes supported by chiral diolate ligands. X-ray crystal structures of [({eta}-C{sub 5}Me{sub 5})TiCl({mu}-{eta}{sup 1},{eta}{sup 1}-2-CF{sub 3}-dpbd)]{sub 2} and [HNEt{sub 3}][({eta}-C{sub 5}Me{sub 5}){sub 2}Zr{sub 2}Cl{sub 2}({mu}-Cl)({mu}-{eta}{sup 1},{eta}{sup 2}-3,5-Me{sub 2}-dpbd){sub 2}]
- Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.
Reaction of optically pure (S,S)-butadiene diepoxide (1) with 2 equiv of Grignard reagent ArMgBr (Ar = 2-CF{sub 3}C{sub 6}H{sub 4} or 3,5-Me{sub 2}C{sub 6}H{sub 3}) in the presence of copper(I) iodide produces the chiral substituted diphenylbutanediols (dpbd) (2S,3S)-ArCH{sub 2}CH(OH)CH(OH)CH{sub 2}Ar (Ar - 2-CF{sub 3}C{sub 6}H{sub 4} (2), abbreviated 2-CF{sub 3}-dpbdH{sub 2}; Ar = 3,5-Me{sub 2}C{sub 6}H{sub 3} (3), abbreviated 3,5-Me{sub 2}-dpbdH{sub 2}). The mono(pentamethylcyclopentadienyl) halide complex ({eta}-C{sub 5}Me{sub 5})TiCl{sub 3} reacts with 1 equiv of diol 2 in the presence of triethylamine to produce the dimeric species [({eta}-C{sub 5}Me{sub 5})TiCl({mu}-{eta}{sup 1},{eta}{sup 1}-2-CF{sub 3}-dpbd)]{sub 2} (4). An analogous reaction employing the zirconium halide ({eta}-C{sub 5}Me{sub 5})ZrCl{sub 3} and the diol 3 leads to isolation of the salt complex [HNEt{sub 3}][({eta}-C{sub 5}Me{sub 5}){sub 2}Zr{sub 2}Cl{sub 2}({mu}-Cl)({mu}-{eta}{sup 1},{eta}{sup 2}-3,5-Me{sub 2}-dpbd){sub 2}] (5). Compounds 4 and 5 have been subjected to single-crystal X-ray diffraction studies. The solid-state structure of 4 consists of two titanium metal centers, each bearing a pentamethylcyclopentadienyl ligand and a terminal chloride ligand, bridged by two diolate ligands such that a central 10-membered ring is formed.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 316220
- Journal Information:
- Inorganic Chemistry, Vol. 37, Issue 24; Other Information: PBD: 30 Nov 1998
- Country of Publication:
- United States
- Language:
- English
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