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Title: Carbon-fluorine bond cleavage by zirconium metal hydride complexes

Abstract

The use of transition metal complexes to cleave strong carbon-fluorine bonds has blossomed in the past several years. Many late transition metal complexes with electron-donating ligands are believed to undergo oxidative addition to the C-F bond of a fluorinated aromatic group. The zirconium hydride dimer [Cp{sub 2}ZrH{sub 2}]{sub 2} reacts with C{sub 6}F{sub 6} at ambient temperature to give Cp{sub 2}Zr(C{sub 6}F{sub 5})F as the major product along with Cp{sub 2}ZrF{sub 2}, C{sub 6}F{sub 5}H and H{sub 2}. Neither the reaction rate nor the product ratio is affected by changes in H{sub 2} pressure or the concentration of C{sub 6}F{sub 6}. The reaction follows zero-order kinetics. The new compound Cp{sub 2}Zr(C{sub 6}F{sub 5})F has been structurally characterized. [Cp{sub 2}ZrH{sub 2}]{sub 2} reacts with C{sub 6}F{sub 5}H to give Cp{sub 2}Zr(p-C{sub 6}F{sub 4}H)F, Cp{sub 2}ZrF{sub 2}, C{sub 6}F{sub 4}H{sub 2}, and H{sub 2}. The zirconium hydride Cp{sub 3}ZrH has been structurally characterized and also reacts with C{sub 6}F{sub 6}. The products of the reaction are CpH, Cp{sub 2}Zr(C{sub 6}F{sub 5})F, C{sub 6}F{sub 5}H, Cp{sub 2}ZrF{sub 2}, Cp{sub 4}Zr, and Cp{sub 3}ZrF. The reaction rate is first order in [Cp{sub 3}ZrH] and [C{sub 6}F{sub 6}], but the product ratio is unaffected bymore » the concentration of C{sub 6}F{sub 6}. Possible mechanisms of these reactions are discussed.« less

Authors:
; ; ;  [1]
  1. Univ. of Rochester, NY (United States). Dept. of Chemistry
Publication Date:
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
682123
DOE Contract Number:  
FG02-86ER13569
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 18; Journal Issue: 16; Other Information: PBD: 2 Aug 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ZIRCONIUM HYDRIDES; CARBON FLUORIDES; CLEAVAGE; CHEMICAL BONDS; KINETICS; CRYSTAL STRUCTURE

Citation Formats

Edelbach, B.L., Rahman, A.K.F., Lachicotte, R.J., and Jones, W.D. Carbon-fluorine bond cleavage by zirconium metal hydride complexes. United States: N. p., 1999. Web. doi:10.1021/om9902481.
Edelbach, B.L., Rahman, A.K.F., Lachicotte, R.J., & Jones, W.D. Carbon-fluorine bond cleavage by zirconium metal hydride complexes. United States. doi:10.1021/om9902481.
Edelbach, B.L., Rahman, A.K.F., Lachicotte, R.J., and Jones, W.D. Mon . "Carbon-fluorine bond cleavage by zirconium metal hydride complexes". United States. doi:10.1021/om9902481.
@article{osti_682123,
title = {Carbon-fluorine bond cleavage by zirconium metal hydride complexes},
author = {Edelbach, B.L. and Rahman, A.K.F. and Lachicotte, R.J. and Jones, W.D.},
abstractNote = {The use of transition metal complexes to cleave strong carbon-fluorine bonds has blossomed in the past several years. Many late transition metal complexes with electron-donating ligands are believed to undergo oxidative addition to the C-F bond of a fluorinated aromatic group. The zirconium hydride dimer [Cp{sub 2}ZrH{sub 2}]{sub 2} reacts with C{sub 6}F{sub 6} at ambient temperature to give Cp{sub 2}Zr(C{sub 6}F{sub 5})F as the major product along with Cp{sub 2}ZrF{sub 2}, C{sub 6}F{sub 5}H and H{sub 2}. Neither the reaction rate nor the product ratio is affected by changes in H{sub 2} pressure or the concentration of C{sub 6}F{sub 6}. The reaction follows zero-order kinetics. The new compound Cp{sub 2}Zr(C{sub 6}F{sub 5})F has been structurally characterized. [Cp{sub 2}ZrH{sub 2}]{sub 2} reacts with C{sub 6}F{sub 5}H to give Cp{sub 2}Zr(p-C{sub 6}F{sub 4}H)F, Cp{sub 2}ZrF{sub 2}, C{sub 6}F{sub 4}H{sub 2}, and H{sub 2}. The zirconium hydride Cp{sub 3}ZrH has been structurally characterized and also reacts with C{sub 6}F{sub 6}. The products of the reaction are CpH, Cp{sub 2}Zr(C{sub 6}F{sub 5})F, C{sub 6}F{sub 5}H, Cp{sub 2}ZrF{sub 2}, Cp{sub 4}Zr, and Cp{sub 3}ZrF. The reaction rate is first order in [Cp{sub 3}ZrH] and [C{sub 6}F{sub 6}], but the product ratio is unaffected by the concentration of C{sub 6}F{sub 6}. Possible mechanisms of these reactions are discussed.},
doi = {10.1021/om9902481},
journal = {Organometallics},
number = 16,
volume = 18,
place = {United States},
year = {1999},
month = {8}
}