2003-06-01, English, Article, Journal or magazine article edition: Substituent effects in oxime radical cations. 1. Photosensitized reactions of acetophenone oximes.(Author Abstract) de Lijser, H.J. Peter; Kim, Jason S.; McGrorty, Suzanne M.; ...

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Physical Description
  • Author Abstract
  • Magazine/​Journal article
Published
  • NRC Research Press, 2003 June
Language
  • English

Edition details

Title
  • Substituent effects in oxime radical cations. 1. Photosensitized reactions of acetophenone oximes.(Author Abstract)
Also Titled
  • Substituent effects in oxime radical cations. 1. Photosensitized reactions of acetophenone oximes.
Appears In
  • Canadian Journal of Chemistry, v.81, no.6, 2003 June, p.575(11) (ISSN: 0008-4042)
Author
  • de Lijser, H.J. Peter
  • Kim, Jason S.
  • McGrorty, Suzanne M.
  • Ulloa, Erin M.
Published
  • NRC Research Press, 2003 June
Physical Description
  • Author Abstract
  • Magazine/​Journal article
Subjects
Target Audience
  • Academic
Summary
  • A variety of ortho-, meta-, and para-substituted (-H, -F, -Cl, -C[F.sub.3], -CN (meta and para only), -C[H.sub.3], -OC[H.sub.3], and -N[O.sub.2]) acetophenone oximes were synthesized and studied using laser flash photolysis (LFP) and steady-state photolysis experiments in acetonitrile with chloranil as the photosensitizer. In addition, semi-empirical (AM1) calculations were performed on the neutral species, the radical cations, and the corresponding iminoxyl radicals. The data was analyzed in terms of the electrochemical peak potentials of the oximes, the quenching rates of triplet chloranil (LFP), the calculated ionization potentials, and the measured conversions of the oximes in the steady-state photolysis experiments. Photolysis of the oximes in the presence of chloranil results in the formation of the chloranil radical anion, which reacts rapidly with the oxime radical cation to form the semiquinone radical and an iminoxyl radical. Evidence for the formation of the chloranil radical anion and the semiquinone radical was obtained from LFP studies. The measured quenching rates from the LFP studies represent the rates of electron transfer from the oximes to triplet chloranil. This data was correlated to various radical and polar substituent constants. The Hammett studies suggest that steric, polar, and radical effects are important for ortho-substituted acetophenone oximes, polar effects are important for para-substituted oximes, and radical stabilization is more important than polar effects for the meta-substituted substrates. The calculated ionization potentials of the oximes show an excellent correlation with the measured quenching rates supporting the electron transfer pathway. On the basis of calculated charge densities, we conclude that the measured substituent effects are transition state effects rather than ground state effects. At this point all of the available data suggests that the conversion of the oximes is controlled by two energetically opposing reactions, namely oxidation of the neutral oxime, which is favorable for oximes with electron-donating substituents, and deprotonation of the oxime radical cation, which is favorable for oximes with electron-withdrawing substituents. The overall result is a reaction with little selectivity as far as substituent effects are concerned. Key words: oxime, radical cation, iminoxyl radical, electron transfer, substituent effect.
Terms of Use
  • COPYRIGHT 2003 NRC Research Press
Language
  • English
Database
  • Gale Academic OneFile
  • Gale General OneFile
  • Gale Expanded Academic
Identifier
  • 109178877

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Bialik College. Bialik College Library. Not open to the public Periodical; Journal, magazine, other English; French
CAVAL. CARM Centre. May not be open to the public brn.181082; Held; Vol. 52, no. 1 - v. 77; Jan. 1974 - 1999; Inc. Periodical; Journal, magazine, other English; French
Charles Sturt University. CSU Library - Electronic Resources (shared). Open to the public 000098168; Full Text Available; ProQuest Natural Science Journals New Platform - Available from 1998 until 2007 Periodical; Journal, magazine, other English; French
Cumberland Council. Auburn Library. Open to the public Periodical; Journal, magazine, other English; French
Defence Science and Technology Group. DST Group Research Information Services - Melbourne. Not open to the public Serials; Vol. 29-v.68; 1951-1990; incomplete Periodical; Journal, magazine, other English; French
Department of Agriculture and Fisheries Qld. Dept of Agriculture and Fisheries Qld Research Information Service. Not open to the public STACK; vol.29,no.1-v.31; 1951-1953 Periodical; Journal, magazine, other English; French
Edith Cowan University. Edith Cowan University Library. Open to the public Periodical; Journal, magazine, other English; French
Flinders University. Flinders University Central Library. Open to the public 9957369701771; 540.5 C21 Periodical; Journal, magazine, other English; French
James Cook University. Townsville Campus Library. Open to the public 104; <104>; Vol. 29 - v. 74; 1951 - 1996; Incomplete Periodical; Journal, magazine, other English; French
Macquarie University. Macquarie University Library. Open to the public 992055610802171; QD1 .C285; Vol. 29 (1951)-vol. 33 (1955); vol. 39 (1961)-vol. 83, no. 8 (2005); vol. 83, no. 10 (2005)-vol. 83, no. 12 (2005) Periodical; Journal, magazine, other English; French
Monash University. Monash University Library. Open to the public 99867301751; 540.5 C212; v. 29 (1951) to v.84 (2006) ; Incomplete ; Includes Indexes; Lacks: v. 52 (1974) ; v. 53, no. 1-6 (1975) ; v. 53, no. 13-24 (1975) ; v.54 (1976) to v. 55 (1977) ; v. 73 (1995) to v. 77 (1999); HA; XST-TE Periodical; Journal, magazine, other English; French
National Library of Australia. Open to the public 2333488; S 540.5 CAN; Vol. 29-v. 64 (1951-1986) Periodical; Journal, magazine, other English; French
NSW Department of Industry. DTIRIS: Electronic Resources Library. Not open to the public V 29 1951 - V 75 1997 Periodical; Journal, magazine, other English; French
RMIT University. RMIT University Library. Open to the public 9912892330001341; PER 540 C212; Incomplete. Held in Storage. Request from <a href=http://www.rmit.edu.au/library/dds target=_blank>Document Delivery</a>; v. 51, no. 1 (Jan. 1, 1973)-v. 70, no. 12 (Dec. 1992) Periodical; Journal, magazine, other English; French
Shellharbour City Council. Shellharbour City Library Service. Open to the public Periodical; Journal, magazine, other English; French
Shore School. Boer War Contingent Memorial Library. Not open to the public Periodical; Journal, magazine, other English; French
Southern Cross University. University Library Lismore. Open to the public Electronic resource - Check catalogue for holdings Periodical; Journal, magazine, other English; French
State Library of NSW. Open to the public Held; 1951-1991 Periodical; Journal, magazine, other English; French
St Hilda's Anglican School for Girls. St Hilda's Library. May not be open to the public Periodical; Journal, magazine, other English; French
St Vincent's Hospital (Sydney). Walter McGrath Library. Not open to the public (EbpS)ebs515368; held Periodical; Journal, magazine, other English; French
The University of Melbourne. The University Library. Open to the public Ch P CANA; v.29-v.84; 1951-2006 Periodical; Journal, magazine, other English; French
The University of Sydney. University of Sydney Library. Open to the public .b1156507x; held Periodical; Journal, magazine, other English; French
University of Adelaide. Barr Smith Library. Open to the public 9996397001811; MICROFICHE PER 86; v.60(1982)-v.69(1991) Periodical; Journal, magazine, other English; French
University of Newcastle. University of Newcastle Library. Open to the public 540.5/9; Vol. 29, no. 1-v. 75, no. 12; Jan. 1951-Dec. 1997 Periodical; Journal, magazine, other English; French
University of New England. Dixson Library. Open to the public 1024-67060; <1024-67060>; P540.5/CAN <1024-67060>; V.29 (1951)- Periodical; Journal, magazine, other English; French
University of Tasmania. Open to the public .b10389556; Scien ser v29-74;1951-96 Periodical; Journal, magazine, other English
University of Western Australia. University of Western Australia Library. Open to the public 9944031702101; HELD; V. 76-92 ; 1998-2014; V. 49-75 ; 1971-1997 Periodical; Journal, magazine, other English; French
Unknown library code: NWU. Online access. Not available for document delivery Periodical; Journal, magazine, other English; French
Western Sydney University. Campbelltown Campus Library. Open to the public 399266; 540.5 4 Periodical; Journal, magazine, other English; French
Western Sydney University. Penrith Campus Library. Open to the public 399266; Online version Periodical; Journal, magazine, other English; French
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National Library of Australia. Open to the public 2333488; S 540.5 CAN; Vol. 29-v. 64 (1951-1986) Periodical; Journal, magazine, other English; French
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These 15 locations in New South Wales:

Library Access Call number(s) Formats held Language
Charles Sturt University. CSU Library - Electronic Resources (shared). Open to the public 000098168; Full Text Available; ProQuest Natural Science Journals New Platform - Available from 1998 until 2007 Periodical; Journal, magazine, other English; French
Cumberland Council. Auburn Library. Open to the public Periodical; Journal, magazine, other English; French
Macquarie University. Macquarie University Library. Open to the public 992055610802171; QD1 .C285; Vol. 29 (1951)-vol. 33 (1955); vol. 39 (1961)-vol. 83, no. 8 (2005); vol. 83, no. 10 (2005)-vol. 83, no. 12 (2005) Periodical; Journal, magazine, other English; French
NSW Department of Industry. DTIRIS: Electronic Resources Library. Not open to the public V 29 1951 - V 75 1997 Periodical; Journal, magazine, other English; French
Shellharbour City Council. Shellharbour City Library Service. Open to the public Periodical; Journal, magazine, other English; French
Shore School. Boer War Contingent Memorial Library. Not open to the public Periodical; Journal, magazine, other English; French
Southern Cross University. University Library Lismore. Open to the public Electronic resource - Check catalogue for holdings Periodical; Journal, magazine, other English; French
State Library of NSW. Open to the public Held; 1951-1991 Periodical; Journal, magazine, other English; French
St Vincent's Hospital (Sydney). Walter McGrath Library. Not open to the public (EbpS)ebs515368; held Periodical; Journal, magazine, other English; French
The University of Sydney. University of Sydney Library. Open to the public .b1156507x; held Periodical; Journal, magazine, other English; French
University of Newcastle. University of Newcastle Library. Open to the public 540.5/9; Vol. 29, no. 1-v. 75, no. 12; Jan. 1951-Dec. 1997 Periodical; Journal, magazine, other English; French
University of New England. Dixson Library. Open to the public 1024-67060; <1024-67060>; P540.5/CAN <1024-67060>; V.29 (1951)- Periodical; Journal, magazine, other English; French
Unknown library code: NWU. Online access. Not available for document delivery Periodical; Journal, magazine, other English; French
Western Sydney University. Campbelltown Campus Library. Open to the public 399266; 540.5 4 Periodical; Journal, magazine, other English; French
Western Sydney University. Penrith Campus Library. Open to the public 399266; Online version Periodical; Journal, magazine, other English; French
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Department of Agriculture and Fisheries Qld. Dept of Agriculture and Fisheries Qld Research Information Service. Not open to the public STACK; vol.29,no.1-v.31; 1951-1953 Periodical; Journal, magazine, other English; French
James Cook University. Townsville Campus Library. Open to the public 104; <104>; Vol. 29 - v. 74; 1951 - 1996; Incomplete Periodical; Journal, magazine, other English; French
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These 2 locations in South Australia:

Library Access Call number(s) Formats held Language
Flinders University. Flinders University Central Library. Open to the public 9957369701771; 540.5 C21 Periodical; Journal, magazine, other English; French
University of Adelaide. Barr Smith Library. Open to the public 9996397001811; MICROFICHE PER 86; v.60(1982)-v.69(1991) Periodical; Journal, magazine, other English; French
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University of Tasmania. Open to the public .b10389556; Scien ser v29-74;1951-96 Periodical; Journal, magazine, other English
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Bialik College. Bialik College Library. Not open to the public Periodical; Journal, magazine, other English; French
CAVAL. CARM Centre. May not be open to the public brn.181082; Held; Vol. 52, no. 1 - v. 77; Jan. 1974 - 1999; Inc. Periodical; Journal, magazine, other English; French
Defence Science and Technology Group. DST Group Research Information Services - Melbourne. Not open to the public Serials; Vol. 29-v.68; 1951-1990; incomplete Periodical; Journal, magazine, other English; French
Monash University. Monash University Library. Open to the public 99867301751; 540.5 C212; v. 29 (1951) to v.84 (2006) ; Incomplete ; Includes Indexes; Lacks: v. 52 (1974) ; v. 53, no. 1-6 (1975) ; v. 53, no. 13-24 (1975) ; v.54 (1976) to v. 55 (1977) ; v. 73 (1995) to v. 77 (1999); HA; XST-TE Periodical; Journal, magazine, other English; French
RMIT University. RMIT University Library. Open to the public 9912892330001341; PER 540 C212; Incomplete. Held in Storage. Request from <a href=http://www.rmit.edu.au/library/dds target=_blank>Document Delivery</a>; v. 51, no. 1 (Jan. 1, 1973)-v. 70, no. 12 (Dec. 1992) Periodical; Journal, magazine, other English; French
The University of Melbourne. The University Library. Open to the public Ch P CANA; v.29-v.84; 1951-2006 Periodical; Journal, magazine, other English; French
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