BREDT RULE KINETICALLY STABILIZED NITROGEN-CENTERED RADICAL CATIONS AND RADICALS IN THE 9-AZABICYCLO[3.3.1]NONYL SYSTEM
BREDT RULE KINETICALLY STABILIZED NITROGEN-CENTERED RADICAL CATIONS AND RADICALS IN THE 9-AZABICYCLO[3.3.1]NONYL SYSTEM
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DOI：
10.1021/ja00522a044
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
BRIEN, DJ
中科院分区：
文献类型：
--
作者：
NELSEN, SF;KESSEL, CR;BRIEN, DJ
9-氮杂双环[3.3. 1]研究了Ng上取代基为CR ~ 3、NR ~ 2、OR、Cl、β ~（3+）和羰基的壬烷（9-ABN）和双键亚胺盐（9-ABN= Y）~+（其中Y= CRR ′、NR ′和O）与9-ABN取代的对苯二胺、2-四氮烯和4-叔丁基苯胺的沿着反应。9-Ze-正丁基-9-ABN在Ng处具有强的酰胺键，并提出了一种由PE数据估算胺在Ng处的结晶度的方法。这些化合物的循环伏安法数据，其中许多给出足够稳定的单电子氧化或还原产物的E '测量，和PE数据给出的中性化合物。氧化形式可以被认为是通过直接连接的X：或Y· Ng取代基稳定的R2 N·基团。测定的相对电子转移AG值范围为87千卡/摩尔，取决于Ng取代基。如果假设\是适当地代表场效应的取代基，这些数据允许估计的差异，在共振稳定的两个原子系统的氧化和还原形式（ARS）。所得ARS值（kcal/mol）包括4（X= Z-Bu），8（CsEU-Z-Bu），10-14（OMe），19（β 2），约. 20（O·），ca. 42（E-Z-Bu）and ca. 58（CH-Z-Bu）。对于文献比较是可能的唯一情况，四烷基肼自由基阳离子，上述估计是在良好的协议。
Derivatives of 9-azabicyclo [3.3. 1] nonane (9-ABN) where the substituent at Ng is CR3, NR2, OR, Cl, ß3+, and carbonyl, and of doublybonded immonium salts (9-ABN= Y)+, where Y= CRR', NR', and O, were studied, along with 9-ABN-substituted p-phenylenediamine, 2-tetrazene, and 4-rez-r-butylaniline. 9-Ze «-Butyl-9-ABN is argued to be strongly py-ramidal at Ng, and a methodology for estimating pyramidality at nitrogenof amines from PE data is described. Cyclic voltammetry data are reported for these compounds, many of which give stable enough one-electron oxidation or reduction products for E'measurement, and PE data are given for the neutral compounds. The oxidized forms may be considered R2N" 1"· groups stabilized by directly attached X: or Y· Ng substituents. The relative electron transfer AGvalues measured cover a range of 87 kcal/mol, depending on Ng substituent. If\is assumed to properly represent field effects of the substituents, these data allow estimation of the difference in resonance stabilization of thetwo-atom system for the oxidized and reduced forms (ARS). ARS values obtained (kcal/mol) include 4 (X= Z-Bu), 8 (CsEU-Z-Bu), 10-14 (OMe), 19 (ß2), ca. 20 (O·), ca. 42 (Ñ-Z-Bu) and ca. 58 (CH-Z-Bu). For the only case in which literature comparison is possible, tetraalkylhydrazine radical cat-ions, the above estimate is in good agreement.