Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 3215 - 3222 (1988)
Update date:2022-09-26
Topics:
Rhodes, Christopher J.
Radical cations of azoalkanes have been observed for the first time in low-temperature matrix by e.s.r. spectroscopy.The e.s.r. data show that they are ?-cations despite photoelectron studies which indicate the HOMO for an azoalkane to be the ? (n-) orbital.Interestingly, these species appear to be stable, at least up to ca. 160 K, and show no tendency to fragment to form alkyl radicals.This contrasts with the solution-phase behaviour of these species, which are intermediates in the oxidation of azoalkanes, and give rise to carbocations and alkyl radicals.Imines form similar ?-radical cations which show a greater tendency to decompose.The structures and stabilities of these cations are discussed.Attempts to observe the corresponding azoalkane anions in solid matrices resulted only in the formation of alkyl radicals, and so we conclude that the anions decompose by fragmentation, although they have been studied in solution under steady-state conditions.Previously derived coupling parameters predict isotropic 14N hyperfine couplings for these species which are larger than those observed.Therefore, new values are calculated, and these fit well with the observed couplings.In this way, spin polarisation parameters are obtained for individual contributions to the couplings, as opposed to previous approaches which treat them collectively.
View MoreNIGNXIA XINDACHANG TECHNOLOGY CO.,LTD
Contact:86-0951-7815345
Address:North side of Qiyuan Road, west side of Yuanfeng Highway, New Material Park, Ningdong Energy and Chemical Industry Base, Ningxia,China
Suzhou SuKaiLu Chemical Technology Co., Ltd.
Contact:+86-512-62766020
Address:Floor 4, Building 1, Xinyi Pharmaceutical Valley Wisdom Industrial Park, 415 Changyang Street, Suzhou Industrial Park, Jiangsu Province
website:http://www.oceanchem-group.com
Contact:86-536-8596048
Address:9th floor,Building B future Plaza, No.88.Fenghuang Street,Weifang,Shandong,China
Qingdao Kingway Pharmtech Co., Ltd.
Contact:86-532-87118899
Address:No. 88, Middle Haixi Road, Jiaonan City, Qingdao, China
Suzhou Credit International Trading Co., Ltd
Contact:+86-512-65398039
Address:Qingdeng, Hightech. District, Suzhou
Doi:10.1021/ja01230a013
(1944)Doi:10.3390/molecules26041141
(2021)Doi:10.1248/cpb.27.2544
(1979)Doi:10.1021/jo01298a040
(1980)Doi:10.1016/S0040-4039(01)95518-2
(1979)Doi:10.1007/BF00938727
(1980)
