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  Home > JCE Print > Journal of Chemical Education > Issues > 2007  > September  >
In the Laboratory
Determining the Quantum Efficiency for Activation of an Organometallic Photoinitiator for Cationic Polymerization
An Experiment for the Physical or Inorganic Chemistry Laboratory
David M. Hayes, Maura Mahar, R. Chris Schnabel, and Paras Shah
Department of Chemistry, Union College, Schenectady, NY 12308

Alistair J. Lees and Vladimir Jakubek
Department of Chemistry, Binghamton University, Binghamton, NY 13902-6000

Cover
September 2007
Vol. 84 No. 9
p. 1483

Abstract
We present a new laboratory experiment on the photochemistry of organometallic η56-mixed-sandwich compounds, which is suitable for both the physical chemistry and inorganic chemistry laboratory. Specifically, students use 1,10–phenanthroline to trap the intermediate formed when [CpFe(isopropylbenzene)]PF6 is photolyzed with 458 nm light from an argon–krypton laser. Using quantitative UV–vis spectroscopy students then determine the quantum yield of arene ring displacement from the mixed-sandwich complex. The photogenerated intermediate, [CpFe(solvent)3]+ is an efficient initiator for the polymerization of epoxides, dicyanate esters, pyrrole, styrene, dioxolenes, and acrylates. The efficiency with which the intermediate is photochemically formed is therefore an important property in determining its commercial utility. Although the experiment can easily be done in one 3–4 hour laboratory period, it readily lends itself to broadening into a multi-week research project. In this mode, students can examine how changing the nature of the solvent and the irradiation wavelength affect the quantum yield of reaction. Such information can be used to reveal the role of the solvent in the reaction and the electronic excited states from which reaction occurs. Furthermore, in the inorganic laboratory, students could be asked to synthesize [CpFe(isopropylbenzene]PF6 before looking at its photochemical behavior, thus gaining experience in working under air-free conditions.
Supplement
Instructions for students and notes for the instructor, including an appendix deriving and discussing eq 1, are available.
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Citation
Hayes, David M.; Lees, Maura; Schnabel, R. Chris; Shah, Paras; Alistair J.; Jakubek, Vladimir; Mahar. J. Chem. Educ. 2007, 84, 1483.
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Keywords
Computer-Based Learning; Hands-On Learning / Manipulatives; Inorganic Chemistry; Kinetics; Laboratory Instruction; Organometallics; Photochemistry; Physical Chemistry; Reactive Intermediates; Transition Elements; Upper-Division Undergraduate; UV-Vis Spectroscopy
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History
Created:
Last Updated:
7/23/2007
8/16/2007
 Caution! 
Experiments, laboratory exercises, lecture demonstrations, and other descriptions of the use of chemicals, apparatus, instruments, computers, and computer interfaces are presented in the Journal of Chemical Education as illustrative of new or improved ideas or concepts in chemistry instruction and are directed at qualified teachers. Although every effort is made to assure and encourage safe practices and safe use of chemicals, the Journal of Chemical Education cannot assume responsibility for uses made of its published materials. Many chemicals are hazardous. Precautions for the safe use of hazardous chemicals and directions for their proper disposal are described in the Material Safety Data Sheets and on the labels. We strongly urge all those planning to use materials from our pages to make choices and to develop procedures for laboratory and classroom safety in accordance with local needs and situations.
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