Cookies Policy
X

This site uses cookies. By continuing to browse the site you are agreeing to our use of cookies.

I accept this policy

Find out more here

Isomerization of Unsaturated Radicals. Vi. Isomerization of 3-Cyclopentenyl and Pentamethylene Radicals

No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
The full text of this article is not currently available.

Brill’s MyBook program is exclusively available on BrillOnline Books and Journals. Students and scholars affiliated with an institution that has purchased a Brill E-Book on the BrillOnline platform automatically have access to the MyBook option for the title(s) acquired by the Library. Brill MyBook is a print-on-demand paperback copy which is sold at a favorably uniform low price.

This Article is currently unavailable for purchase.
Add to Favorites
You must be logged in to use this functionality

Cover image Placeholder

The 184.9 nm photochemistry of gaseous 3-methylcyclopentene and 3-methyl-1,4-pentadiene have been studied. Both photoexcited species decompose mainly through the primary rupture of the C-CH3 bond. Vibrationally excited 3-cyclopentenyl and pentamethylene radicals are formed in the primary decomposition in the former and latter systems respectively. These radicals are connected through isomerization reactions: in the presence of DI, the isomers cyclopentene, and trans-1,3-pentadiene and/or vinylcyclopropane are formed in both systems. The quantum yields depend on the pressure and the starting monomer: cyclopentene and cyclopentadiene are the major products from the photolysis of 3-methylcyclopentene + DI mixtures and only minor quantities of the other C5H8 compounds are formed. Cyclopentadiene is the major product of the photolysis of 3-methyl-1,4-pentadiene + O2 mixtures whereas vinylcyclopropane and trans-1,3-pentadiene are the major C5 products of the photolysis of 3-methyl-1,4-pentadiene + DI mixtures. The geometries of 3-cyclopentenyl and of the structures at the six critical points in the torsional potential energy curve (TPEC) for rotation about the 2- and 3-C-C bonds in the open chain pentamethylene species have been optimized completely by ab initio RHF-SCF gradient methods. For the open-chain structures the bond orders, bond lengths and the free valence (primarily associated with the central carbon atom) all correspond to 1,4-pentadien-3-yl conformations. In the ground state there is a high barrier to formation of 3-cyclopentenyl from 1,4-pentadien-3-yl. The features (relative energies and torsional barriers) of the TPEC for 1,4-pentadien-3-yl explain the ESR observations for the open chain C5H7 radical rotamers.

Affiliations: 1: Laboratoire de Chimie Physique Moléculaire Faculté des Sciences CP. 160 Université Libre de Bruxelles 50, av. F.D. Roosevelt, B-1050 Brussels, Belgium; 2: Département des Sciences Fondamentales Université du Québec à Chicoutimi (UQAC) Chicoutimi, Québec, Canada G7H 2B1

10.1163/156856790X00229
/content/journals/10.1163/156856790x00229
dcterms_title,pub_keyword,dcterms_description,pub_author
10
5
Loading
Loading

Full text loading...

/content/journals/10.1163/156856790x00229
Loading

Data & Media loading...

http://brill.metastore.ingenta.com/content/journals/10.1163/156856790x00229
Loading

Article metrics loading...

/content/journals/10.1163/156856790x00229
2017-12-17

Sign-in

Can't access your account?
  • Key

  • Full access
  • Open Access
  • Partial/No accessInformation