An Azobenzenyl Anion Radical Complex of Magnesium: Synthesis, Structure, and Reactivity Studies
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Azobenzenyl anion radical complex of magnesium [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(PhNNPh) (THF) (2) was obtained for the first time through the reaction of [HC(C(Me)N-2,6-iPr2C6H3)2]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 Me3SiN3 yielding the magnesium thiolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SPh)(THF) (3), magnesium selenolate [HC(C(Me)N-2,6-iPr2C6H3)2]Mg(SePh)(THF) (4), peroxido complex {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(THF)}2(μ–η2-η2-O2) (5), persulfido complex {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg(THF)}2(μ–η2-η2-S2) (6), and azido complex [HC(C(Me)N-2,6-iPr2C6H3)2]MgN3 (7), respectively. Furthermore, treatment of 2 with Me3SiCHN2 results in a rearrangement product {[HC(C(Me)N-2,6-iPr2C6H3)2]Mg[CNN(SiMe3)]}2 (8).
创建时间:
2016-11-15



