Ren Wenshan, Gu Defa
College of Chemistry and Chemical Engineering, Southwest University , Chongqing 400715, China.
Inorg Chem. 2016 Nov 21;55(22):11962-11970. doi: 10.1021/acs.inorgchem.6b02114. Epub 2016 Nov 1.
Azobenzenyl anion radical complex of magnesium [HC(C(Me)N-2,6-PrCH)]Mg(PhNNPh) (THF) (2) was obtained for the first time through the reaction of [HC(C(Me)N-2,6-PrCH)]MgBr (1) with potassium graphite in the presence of azobenzene. Complex 2 is a useful electron-transfer reagent as shown by the reactivity with diphenyl disulfide, diphenyl diselenide, oxygen, sulfur, and MeSiN yielding the magnesium thiolate [HC(C(Me)N-2,6-PrCH)]Mg(SPh)(THF) (3), magnesium selenolate [HC(C(Me)N-2,6-PrCH)]Mg(SePh)(THF) (4), peroxido complex {[HC(C(Me)N-2,6-PrCH)]Mg(THF)}(μ-η-η-O) (5), persulfido complex {[HC(C(Me)N-2,6-PrCH)]Mg(THF)}(μ-η-η-S) (6), and azido complex [HC(C(Me)N-2,6-PrCH)]MgN (7), respectively. Furthermore, treatment of 2 with MeSiCHN results in a rearrangement product {[HC(C(Me)N-2,6-PrCH)]Mg[CNN(SiMe)]} (8).
镁的偶氮苯阴离子自由基配合物[HC(C(Me)N - 2,6 - PrCH)]Mg(PhNNPh)(THF)(2)首次通过[HC(C(Me)N - 2,6 - PrCH)]MgBr(1)与钾石墨在偶氮苯存在下反应制得。配合物2是一种有用的电子转移试剂，这可由其与二苯基二硫、二苯基二硒、氧气、硫和MeSiN的反应得到证明，分别生成硫醇镁盐[HC(C(Me)N - 2,6 - PrCH)]Mg(SPh)(THF)(3)、硒醇镁盐[HC(C(Me)N - 2,6 - PrCH)]Mg(SePh)(THF)(4)、过氧配合物{[HC(C(Me)N - 2,6 - PrCH)]Mg(THF)}(μ - η - η - O)(5)、过硫配合物{[HC(C(Me)N - 2,6 - PrCH)]Mg(THF)}(μ - η - η - S)(6)和叠氮配合物[HC(C(Me)N - 2,6 - PrCH)]MgN(7)。此外，用MeSiCHN处理2会得到一种重排产物{[HC(C(Me)N - 2,6 - PrCH)]Mg[CNN(SiMe)]}(8)。
