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Title: 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}]

Abstract

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.

Authors:
; ; ; ;  [1]
  1. Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.
Publication Date:
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
316220
DOE Contract Number:  
W-7405-ENG-36
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 37; Journal Issue: 24; Other Information: PBD: 30 Nov 1998
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; TITANIUM COMPLEXES; ZIRCONIUM COMPLEXES; CRYSTAL STRUCTURE; SYNTHESIS; ORGANOMETALLIC COMPOUNDS; BOND LENGTHS; CATALYSIS

Citation Formats

Clark, D L, Click, D R, Grumbine, S K, Scott, B L, and Watkin, J G. 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}]. United States: N. p., 1998. Web. doi:10.1021/ic980645o.
Clark, D L, Click, D R, Grumbine, S K, Scott, B L, & Watkin, J G. 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}]. United States. doi:10.1021/ic980645o.
Clark, D L, Click, D R, Grumbine, S K, Scott, B L, and Watkin, J G. Mon . "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}]". United States. doi:10.1021/ic980645o.
@article{osti_316220,
title = {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}]},
author = {Clark, D L and Click, D R and Grumbine, S K and Scott, B L and Watkin, J G},
abstractNote = {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.},
doi = {10.1021/ic980645o},
journal = {Inorganic Chemistry},
number = 24,
volume = 37,
place = {United States},
year = {1998},
month = {11}
}