University of Illinois Urbana-Champaign

Photochemical reactions of tetraorganoborate salts: Electron transfer-mediated photoreductions and alkylations and di-pi-borate rearrangements

Kropp, Michael Andrew

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Description

Title
Photochemical reactions of tetraorganoborate salts: Electron transfer-mediated photoreductions and alkylations and di-pi-borate rearrangements
Author(s)
Kropp, Michael Andrew
Issue Date
1990
Doctoral Committee Chair(s)
Schuster, Gary B.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
  • The photochemical reaction of sodium borohydride and methyltriphenylborate with halo-substituted cyanonaphthalenes has been studied. The reaction leads to photo-dehalogenation in high yield. Sodium borohydride was also found to react photochemically with dicyanonaphthalene, leading to reduction products. These reactions are proposed to occur through an initial electron transfer step.
  • Photoalkylations of aryl ketones with alkyltriphenylborates has also been studied. The excited state of the ketone reacts with the borate via electron transfer, yielding addition and reduction products.
  • The direct irradiation of alkyl and aryl borates was investigated. Photolysis of trans-$\beta$-styryltriphenylborate leads to the formation of trans-1,1,2,3-tetraphenylboratirane. Similarly, photolysis of (phenylethynyl)triphenylborate leads to the formation of 1,1,2,3-tetraphenylboratirene. Both of these compounds are believed to be formed via a di-$\pi$-borate rearrangement. These are the first examples of a tetravalent, anionic boron atom contained in a three-membered ring to be isolated and characterized. Both compounds show intriguing properties.
  • Irradiation of (2-phenylcyclopropyl)dimethylphenylborate showed evidence for the formation of a boratetane, a tetravalent boron atom in a four-membered ring.
Type of Resource
text
Permalink
http://hdl.handle.net/2142/22795
Copyright and License Information
Copyright 1990 Kropp, Michael Andrew

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