A stable tetrazagallole and its radical anion dimer

Abstract

The reaction of the carbazole ligand supported Ga(I) compound LGa(THF) (3) and 1-azido-4-(tert-butyl)benzene (ArN3) afforded the first stable tetrazagallole LGaN4Ar2 (4) bearing a three-coordinate Ga atom. Reduction of 4 with...

An Isolable Magnesium(II)-Radical Dianion Complex

“…Analyses of the electronic structures reveal that the bipyridine and diazo ligands are in a radical anion state due to the redox-active properties, and the magnesium center is essentially in the +2 oxidation state. In an attempt to isolate a mononuclear magnesium­(I) compound, we utilized the ligand 3,6-di- tert -butyl-1,8-bis­(10-phenylanthracen-9-yl)­carbazolyl (L – ) as a supporting ligand, which was previously applied by our group to synthesize the Ga­(I) compound LGa­(THF) . Herein, we report the synthesis and characterization of the magnesium compound LMg­(THF) 2 ( 3 ), which turns out to be a Mg­(II)-radical dianion complex as shown by electron paramagnetic resonance (EPR) spectroscopic studies and theoretical calculations, attributed to the redox-noninnocent nature of the anthracenyl unit.…”

A germanimidoyl chloride: synthesis, characterization and reactivity

“…3 may be formed through the [2+3] cycloaddition of a transient GeQN double bonded species with a second equivalent of ArN 3 owing to the insufficient steric protection from the Ar group, reminiscent of the reaction of a Ga(I) compound with ArN 3 . 27 Similar five-membered ring compounds were also obtained in the reactions of tetrelenes with organic azides. [28][29][30] In order to test if the chloride in 3 could be replaced by a weakly coordinating anion to give a germanium cation, which might act as a Lewis acid for small molecule activation and catalysis, 31,32 we carried out the reaction of 3 with 1 molar equivalent of NaBAr The molecular structure of 2 was determined by singlecrystal X-ray diffraction (SC-XRD) analysis (Fig.…”

“…1.22 Å), 18 suggesting electron delocalization over the four nitrogen atoms, in accordance with the electronic structure of a tetrazagallole. 27 With 2 available, we were interested in investigating its functionalization to other GeQN double bond bearing compounds. The salt metathesis reaction of 2 with 3,5-di-tertbutylphenyllithium (Ar 0 Li) in THF at room temperature produced the germanimine M s Fluind tBu -Ge(Ar)QNMes ( 5) as an orange solid in 65% yield (Scheme 1).…”

Exoergic pathways triggered by O/H radicals in different metallic carbohydrazide perchlorates (M2+= Mn2+, Fe2+, Co2+, Ni2+, Zn2+and Cd2+)

“…As modern primary explosives, green energetic complexes are composed of light transition cations and environment-friendly energetic ligands. [1][2][3][4] Compared with the pollution from heavy metals and the mechanical sensitivity of traditional primary explosives such as mercury fulminate or lead azide, 5,6 green energetic complexes are easier to synthesize with environmentfriendly properties and higher thermal stability; [7][8][9] examples include metallic carbohydrazide (CHZ) perchlorate, 10,11 metallic imidazole (IMI) perchlorate and metallic 1,5-diaminotetrazole (DAT) perchlorate. 3,12 As representative environment-friendly primary explosives, many metallic carbohydrazide perchlorate ([M(CHZ) 3 ](ClO 4 ) 2 , MCP) complexes have been synthesized in the last decade, including MnCP, 13 FeCP, 14 CoCP, 15 NiCP, 16 CuCP, 17 ZnCP, 18 CdCP 19 and CaCP, 20 generally with excellent fluidity and moderate sensitivity.…”

“…As modern primary explosives, green energetic complexes are composed of light transition cations and environment-friendly energetic ligands. 1–4 Compared with the pollution from heavy metals and the mechanical sensitivity of traditional primary explosives such as mercury fulminate or lead azide, 5,6 green energetic complexes are easier to synthesize with environment-friendly properties and higher thermal stability; 7–9 examples include metallic carbohydrazide (CHZ) perchlorate, 10,11 metallic imidazole (IMI) perchlorate and metallic 1,5-diaminotetrazole (DAT) perchlorate. 3,12…”