Polynuclear branched tetrazole systems. 3. Acidity of α,ω-ditetrazol-5-ylalkanes

Zubarev, V. Yu.; Trifonov, R. E.; Poborchii, Vladimir; Островский, В. А.

doi:10.1007/s10593-006-0113-3

Cited by 15 publications

(8 citation statements)

References 4 publications

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“…Chelating bis(1H-tetrazol-5-yl)methane 1 was synthesized through a 1,3-dipolar cycloaddition between the commercially available malononitrile and sodium azide as previously reported by Ostrovskii et al (Scheme 1). 39 1 was then deprotonated with different bases to give bistetrazolate dianionic ligands 1a and 1b, which were successfully exploited as bidentate ancillary ligands to prepare three differently cyclometalated anionic iridium(III) complexes, 2− 4 (Scheme 2).…”

Section: ■ Experimental Sectionsupporting

confidence: 76%

Anionic Cyclometalated Iridium(III) Complexes with a Bis-Tetrazolate Ancillary Ligand for Light-Emitting Electrochemical Cells

et al. 2017

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A series of monoanionic Ir(III) complexes (2-4) of general formula [Ir(C^N)(b-trz)](TBA) are presented, where C^N indicates three different cyclometallating ligands (Hppy = 2-phenylpyridine; Hdfppy = 2-(2,4-difluoro-phenyl)pyridine; Hpqu = 2-methyl-3-phenylquinoxaline), b-trz is a bis-tetrazolate anionic N^N chelator (Hb-trz = di(1H-tetrazol-5-yl)methane), and TBA = tetrabutylammonium. 2-4 are prepared in good yields by means of the reaction of the suitable b-trz bidentate ligand with the desired iridium(III) precursor. The chelating nature of the ancillary ligand, thanks to an optimized structure and geometry, improves the stability of the complexes, which have been fully characterized by NMR spectroscopy and high-resolution MS, while X-ray structure determination confirmed the binding mode of the b-trz ligand. Density functional theory calculations show that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) are mainly localized on the metal center and the cyclometalating ligands, while the bis-tetrazolate unit does not contribute to the frontier orbitals. By comparison with selected classes of previously published cationic and anionic complexes with high ligand field and even identical cyclometallating moieties, it is shown that the HOMO-LUMO gap is similar, but the absolute energy of the frontier orbitals is remarkably higher for anionic vs cationic compounds, due to electrostatic effects. 2-4 exhibit reversible oxidation and reduction processes, which make them interesting candidates as active materials for light emitting electrochemical cells, along with red, green, and blue emission, thanks to the design of the C^N ligands. Photoluminescence quantum yields range from 28% (4, C^N = pqu, red emitter) to 83% (3, C^N = dfppy, blue emitter) in acetonitrile, with the latter compound reaching 95% in poly(methyl methacrylate) (PMMA) matrix. In thin films, the photoluminescence quantum yield decreases substantially probably due to the small intersite distance between the complexes and the presence of quenching sites. In spite of this, surprisingly stable electroluminescence was observed for devices employing complex 2, demonstrating the robustness of the anionic compounds.

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Section: ■ Experimental Sectionsupporting

confidence: 76%

Anionic Cyclometalated Iridium(III) Complexes with a Bis-Tetrazolate Ancillary Ligand for Light-Emitting Electrochemical Cells

et al. 2017

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“…One route is the cyclization of malononitrile with sodium azide and dimethylammonium chloride in DMF under reflux. However, purification of the product is complicated . A better route is the [2 + 3] cycloaddition reaction of sodium azide with malononitrile catalyzed by zinc bromide in water according to a modified literature procedure at a temperature of 110 °C (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…The transition metal(II) complexes 2 – 9 were prepared by combining solutions of di(1 H -tetrazol-5-yl)methane ( 1 ) and metal(II) salts in the corresponding acid at room temperature (Scheme ). Due to the acidic character of the ligand (p K a 1 = 3.42, p K a 2 = 5.30), diluted acids were chosen as solvent for the reaction in order to prevent precipitation of the corresponding metal tetrazolate salts. This strategy ensures the incorporation of the neutral nitrogen-rich ligand to build up cationic or neutral complexes with oxidizing anions like nitrates or perchlorates to produce more sensitive energetic materials as possible alternatives for heavy metal free primary explosives.…”

Section: Resultsmentioning

confidence: 99%

Di(1H-tetrazol-5-yl)methane as Neutral Ligand in Energetic Transition Metal Complexes

Freis¹,

Klapötke²,

Stierstorfer³

et al. 2017

Inorg. Chem.

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The synthesis of di(1H-tetrazol-5-yl)methane (1, 5-DTM), starting from commercially available sodium azide and malononitrile, is described. This tetrazole was characterized and investigated for use as a neutral nitrogen-rich ligand in various energetic transition metal complexes: ([CuCl(5-DTM)]·2HO (2), [Co(HO)(5-DTM)]Cl (3), [Ni(HO)(5-DTM)]Cl (4), [Co(HO)(5-DTM)](NO) (6), [Ni(HO)(5-DTM)](NO) (7), [Zn(HO)(5-DTM)](NO) (8), {[Cu(SO)(5-DTM)(HO)(5-DTM)]·2HO} (9), [Cu(HO)(5-DTM)](NO) (11), [Cu(NO)(5-DTM)]·2HO (12), [Cu(NO)(5-DTM)] (13), [Cu(HO)(5-DTM)](ClO) (14), and [Cu(ClO)(5-DTM)] (15). Obtained coordination compounds were characterized using single crystal X-ray diffraction (except for 7 and 13), IR spectroscopy, elemental analysis, and differential thermal analysis. The sensitivities to external stimuli (impact, friction, electrostatic discharge) were determined. Complexes 12 and 13 were tested for their ignitability by laser irradiation.

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“…Following the general procedure using 4 equiv of TMSN 3 , a flash chromatography (eluent DCM/MeOH 9:1 + 0.1% HCO 2 H) afforded 2t (37 mg, 49%). mp 212 °C [lit . 210 °C].…”

Section: Experimental Sectionmentioning

confidence: 99%

Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles by Continuous Flow: Application to the Synthesis of Valsartan

Carpentier

Felpin

Zammattio

et al. 2020

Org. Process Res. Dev.

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An efficient continuous flow process for the synthesis of 5-substituted 1H-tetrazoles is described. The process involves the reaction between a polymer-supported triorganotin azide and organic nitriles. The polymer-supported organotin azide which is in situ generated with a polystyrene-supported triorganotin alkoxide and trimethylsilylazide, is immobilized in a packed bed reactor. This approach is simple, fast (it takes from 7.5 to 15 min) and guarantees a low concentration of tin residues in the products (< 5 ppm). The process was developed to aryl-, heteroaryl-and also alkylnitriles and was applied for the synthesis of valsartan, an angiotensin II receptor antagonist.

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Polynuclear branched tetrazole systems. 3. Acidity of α,ω-ditetrazol-5-ylalkanes

Cited by 15 publications

References 4 publications

Anionic Cyclometalated Iridium(III) Complexes with a Bis-Tetrazolate Ancillary Ligand for Light-Emitting Electrochemical Cells

Anionic Cyclometalated Iridium(III) Complexes with a Bis-Tetrazolate Ancillary Ligand for Light-Emitting Electrochemical Cells

Di(1H-tetrazol-5-yl)methane as Neutral Ligand in Energetic Transition Metal Complexes

Synthesis of 5-Substituted 1H-Tetrazoles from Nitriles by Continuous Flow: Application to the Synthesis of Valsartan

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