Organic Chemistry - Standalone book
Organic Chemistry - Standalone book
10th Edition
ISBN: 9780073511214
Author: Francis A Carey Dr., Robert M. Giuliano
Publisher: McGraw-Hill Education
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Chapter 15, Problem 42DSP

Cyclobutadiene and (Cyclobutadiene)tricarbonyliron

As we saw in Section 12.17 , cyclobutadiene is antiaromatic and exceedingly difficult to prepare and study. Its successful preparation by Rowland Pettit (University of Texas) in 1965 demonstrated how transition-metal organometallic chemistry can provide access to novel reactions and structures. His approach was to prepare cyclobutadiene as a transition-metal complex, then destabilize the complex to trigger its dissociation. The sequence for cyclobutadiene begins with the reaction of cis-3,4- dichlorocyclobutene with diiron nonacarbonyl [ Fe 2 ( CO ) 9 ] . The resulting iron–cyclobutadiene complex satisfies the 18-electron rule, is stable, and undergoes a variety of reactions. Most importantly, oxidation with ceric ammonium nitrate (a source of Ce 4 + ) lowers the electron count from 18 to 16 , causing the complex to dissociate and liberate free cyclobutadiene.

Chapter 15, Problem 42DSP, Cyclobutadiene and (Cyclobutadiene)tricarbonyliron

As we saw in Section, cyclobutadiene is , example  1

Oxidation of (cyclobutadiene)tricarbonyliron with Ce 4 + in the presence of ethyl propynoate yielded a product corresponding to a Diels–Alder adduct of cyclobutadiene and ethyl

propynoate.

Chapter 15, Problem 42DSP, Cyclobutadiene and (Cyclobutadiene)tricarbonyliron

As we saw in Section, cyclobutadiene is , example  2

What is the structure of this product?

Chapter 15, Problem 42DSP, Cyclobutadiene and (Cyclobutadiene)tricarbonyliron

As we saw in Section, cyclobutadiene is , example  3

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Organic Chemistry - Standalone book

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