An Azobenzenyl Anion Radical Complex of Magnesium: Synthesis, Structure, and Reactivity Studies

作者：Ren, Wenshan^*; Gu, Defa

来源：Inorganic Chemistry, 2016, 55(22): 11962-11970.

DOI：10.1021/acs.inorgchem.6b02114

• CRYSTAL-STRUCTURES
• X-RAY
• ELECTROCHEMICAL REDUCTION
• COORDINATION CHEMISTRY
• EPITAXIAL-GROWTH
• LIGANDS
• BOND
• DIMERS
• POLYMERIZATION
• ACTIVATION

Azobenzenyl anion radical complex of magnesium [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]Mg(PhNNPh) (THF) (2) was obtained for the first time through the reaction of [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(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-(Pr2C6H3)-Pr-i)(2)]Mg(SPh)(THF) (3), magnesium selenolate [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]Mg(SePh) (THF) (4), peroxido complex [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]Mg(THF)}(2),(mu-eta(2)-eta(2)-O-2) (5), persulfido complex [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]Mg(THF)}(2).(mu-eta(2)-eta(2)-S-2) (6), and azido complex [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]MgN3 (7), respectively. Furthermore, treatment of 2 with Me3SiCHN2 results in a rearrangement product [HC(C(Me)N-2,6-(Pr2C6H3)-Pr-i)(2)]Mg[CNN ( SiMe3)]}(2) (8).

• 出版日期2016-11-21
• 单位西南大学