Der erste Schritt der Oxidation elementaren Schwefels – die Struktur des Schwefelradikalkations [S<sub>8</sub>]<sup>.+</sup> im Kristall

Derendorf, Janis; Jenne, Carsten; Keßler, Mathias

doi:10.1002/ange.201703083

Cited by 6 publications

(1 citation statement)

References 51 publications

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“…) radical cation was crystallized this way. [18] For monitoring the progress of the reaction as a function of increasing temperature, the reaction ampoules were subsequently heated to 60, 100, and then to 120 °C (333, 373 and 393 K) and kept at this temperature for 6 hours. Raman spectra were recorded through the walls of the ampoules after each halt showing clearly the gradual fading of the bands of (Te 4 ) 2 + (Figure 1).…”

Section: Synthesis Of (Te 7 )[Mf 6 ] 2 M = Nb Ta Under Solvothermal C...mentioning

confidence: 99%

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

Zink,

Zimbardi,

Daniels

et al. 2023

Zeitschrift anorg allge chemie

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Reactions of tellurium with metal pentafluorides MF5 (M=As, Sb, Nb, Ta) in liquid SO2 under supercritical conditions at 160 °C yield (Te7)[MF6]2 containing the polymeric Zintl cation (Te72+)n consisting of chair‐shaped Te6 rings connected via single Te atoms. Crystal structure analyses show all four compounds to crystallize isotopically in the (Te7)[AsF6]2 structure type. Monitoring the reactions via Raman spectra reveal that (Te4)[MF6]2 is formed as an intermediate, which reacts with Te finally to (Te7)[MF6]2. Crystal structures of (Te4)[MF6]2 (M=Nb, Ta) were determined. Microwave assisted solvothermal synthesis give analogous results in very short reaction time. All compounds are also accessible via electrochemical oxidation of Te in presence of [MF6]− as electrolyte. (Te7)[AsF6]2 is a semiconductor with σ=10−7 S/cm at 300 K and an energy for the thermally activated electron process of 0.91 eV. Theoretical calculations on the self‐consistent hybrid DFT level confirm that the fundamental band gap is independent from the kind of M. The frontier orbitals are predominantly composed of Te states. Raman bands at 196, 178, 153, and 138 cm−1 are specific for (Te72+)n. Phonon calculations of (Te7)[TaF6]2 confirm three intensive Raman bands at 210, 174 and 163 cm−1. The corresponding normal modes are mainly localized on (Te7)n.

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Section: Synthesis Of (Te 7 )[Mf 6 ] 2 M = Nb Ta Under Solvothermal C...mentioning

confidence: 99%

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

Zink,

Zimbardi,

Daniels

et al. 2023

Zeitschrift anorg allge chemie

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Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Roemmele

Boeré

2017

ChemElectroChem

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Reaction of the bicyclic sulfur‐nitrogen heterocycles RC6H4CN5S3 (R=4‐CH3O, 4‐CH3, 4‐H, 4‐Cl, 4‐CF3, 3‐CF3) with PR’3 (R′=C6H5 or 4‐CH3OC6H4) produces 3‐phosphoraniminato‐7‐aryl‐1,3,5‐trithia‐2,4,6,8‐tetrazocines RC6H4CN4S3NPR’3. In all cases, only the endo‐isomers were isolated and characterized by 1H, 31P, and 19F NMR as well as UV spectroscopy and X‐ray crystallography. RB3LYP/6‐311+G(d,p)// RB3LYP/6‐31G(d,p) computations were undertaken to help explain the atom‐exact syntheses via intermediates previously detected spectroscopically. Three reasonable intermediates have been computed as stationary points with energies consistent with the observed reaction path. Cyclic and square‐wave voltammetry studies of RC6H4CN4S3NPR’3, using a glassy carbon working electrode in CH2Cl2 with 0.4 M [nBu4N][PF6], reveal two IRR reduction processes at RT in all cases at approximately −1.9 and −2.2 V, respectively, and one IRR oxidation process at approximately +1.0 V (versus Fc+/0). [RC6H4CN4S3NPR’3]−. radical anions (R’=4‐CH3OC6H4, R=4‐CH3O, 4‐H, 4‐CF3) were detected at −50 °C in CH2Cl2 by using in situ electrolysis and simultaneous electron paramagnetic resonance spectroscopy: [4‐RC6H4CN4S3NP(4‐CH3OC6H4)3]−., estimated a(31P)=0.078 mT, a(14N1)=0.031 mT, a(14N2,3)=0.256 mT, a(14N4,5)=0.341 mT. The signals decay rapidly, but after the electrolysis is ended, a persistent EPR signal is always obtained with EPR parameters that match known 4‐aryl‐1,2,3,5‐dithiadiazolyls, that is, a(N)=0.51 mT and g=2.0105, which are consistent with the production of [4‐CF3‐C6H4CN2S2]..

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Synthesis, Electronic Properties and Reactivity of [B₁₂X₁₁(NO₂)]²⁻ (X=F–I) Dianions

Asmis

Beele

Jenne

et al. 2020

Chemistry A European J

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Nitro-functionalized undecahalogenated closo-dodecaborates [B 12 X 11 (NO 2)] 2À were synthesized in high purities and characterized by NMR, IR, and Ramans pectroscopy, single crystal X-diffraction, mass spectrometry,a nd gasphase ion vibrational spectroscopy.T he NO 2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B 12 X 12 ] 2À (X = F-I) dianions evidenced by photoelectron spectroscopy,c yclic voltammetry,a nd quantum-chemical calculations. The stabilizing effect decreasesf rom X = Ft oX= I. Thermogravimetric measurementso ft he salts indicate the loss of the nitric oxide radical(NOC). The homolytic NOC eliminationf rom the dianion under very soft collisionale xcitation in gas-phase ion experiments results in the formation of the radical [B 12 X 11 O] 2À C.T heoretical investigations suggest that the loss of NOC proceeds via the rearrangementp roduct [B 12 X 11 (ONO)] 2À .T he O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formationb yr adicalr ecombination of [B 12 X 11 O] 2À C andN OC is demonstrated.

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Der erste Schritt der Oxidation elementaren Schwefels – die Struktur des Schwefelradikalkations [S₈]^.+ im Kristall

Cited by 6 publications

References 51 publications

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Synthesis, Electronic Properties and Reactivity of [B₁₂X₁₁(NO₂)]²⁻ (X=F–I) Dianions

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Der erste Schritt der Oxidation elementaren Schwefels – die Struktur des Schwefelradikalkations [S8].+ im Kristall

Cited by 6 publications

References 51 publications

The 1D‐Polymeric (Te72+)n in (Te7)[MF6]2 (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

The 1D‐Polymeric (Te72+)n in (Te7)[MF6]2 (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

Synthesis, Electronic Structures, and Electrochemistry of 3‐Triarylphosphoraniminato‐1,3,5‐trithia‐2,4,6,8‐tetrazocines: Detection of Trithiatetrazocinyl Radical Anions

Synthesis, Electronic Properties and Reactivity of [B12X11(NO2)]2− (X=F–I) Dianions

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Der erste Schritt der Oxidation elementaren Schwefels – die Struktur des Schwefelradikalkations [S₈]^.+ im Kristall

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

The 1D‐Polymeric (Te₇²⁺)_n in (Te₇)[MF₆]₂ (M=As, Sb, Nb, Ta) by Solvothermal, Microwave Assisted, and Electrochemical Synthesis

Synthesis, Electronic Properties and Reactivity of [B₁₂X₁₁(NO₂)]²⁻ (X=F–I) Dianions