On the problem of stabilization of α-carbocationic centers in metallocene series. Related interconversions of permethylated α-metallocenylcarbocations and metallocenium cation-radicals of the iron sub-group
using strong Lewisacids E(C6F5)3 (E=B or Al) in combination with metallocenes. In the case of B(C6F5)3, electron transfer to N2O required a powerful reducing agent such as Cp*2Co (Cp*=pentamethylcyclopentadienyl). In the presence of Al(C6F5)3, on the other hand, the reactions could be performed with weaker reducing agents such as Cp*2Fe or Cp2Fe (Cp=cyclopentadienyl). The Lewisacid‐mediated electron
使用强路易斯酸E(C 6 F 5)3(E = B或Al)结合茂金属可实现一氧化二氮(N 2 O)的单电子还原。在B(C 6 F 5)3的情况下,电子转移到N 2 O需要强力的还原剂,例如Cp * 2 Co(Cp * =五甲基环戊二烯基)。另一方面,在存在Al(C 6 F 5)3的情况下,可以用较弱的还原剂如Cp * 2 Fe或Cp 2进行反应。Fe(Cp =环戊二烯基)。路易斯酸介导的电子从茂金属转移到N 2 O导致N-O键断裂,生成N 2和氧基自由基阴离子[OE(C 6 F 5)3 ] ⋅-。后者是高反应性的,并参与CH活化反应。可以通过添加Gomberg二聚体来捕获自由基,该Gomberg二聚体是三苯甲基自由基的来源。
Conversion of the diamagnetic nonamethylferrocenylcarbenium salts into the paramagnetic salts of bis(nonamethylferroceniumyl)ethane
Conversion of the diamagnetic salt of the nonamethylferrocenylcarbenium primary cation into the paramagneticsalt of bis(nonamethylferroceniumyl)ethane has been studied by high-resolution NMR in solution and, mainly, by spin—lattice and spin—spin relaxation in solids. For the first time the dependence of the conversion rate on the nature of the anions BF4−, PF6−, AlBr4− and the aggregate state of the
Kruglova; Kreindlin; Petrovskii, Russian Chemical Bulletin, 1998, vol. 47, # 12, p. 2451 - 2454
作者:Kruglova、Kreindlin、Petrovskii、Rybinskaya
DOI:——
日期:——
Deprotonation of decamethylferrocenium cation — new approach to alkyl group functionalization in transition metal complexes
作者:Lyudmila N. Novikova、Dmitrii V. Zagorevskii、Nikolai A. Ustynyuk
DOI:10.1016/0022-328x(93)80371-h
日期:1993.11
Deprotonation of decamethylferrocenium tetrafluorborate (20-degrees-C, THF, (t)BuOK or iPr2NH, Et3N) proceeds via intermediate formation of nonamethylferrocenylmethyl radical and results in the products of butoxylation and amination of methyl groups.
On the problem of stabilization of α-carbocationic centers in metallocene series. Related interconversions of permethylated α-metallocenylcarbocations and metallocenium cation-radicals of the iron sub-group