Access to Bis-Silylene-Stabilized Group 13 Cations

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

Herein, we report the isolation of pyridine moiety-functionalized SiNSi pincer-based bis-silylene ligand (1) and its reactivity toward various halide precursors (X = Br I) group 13 elements (M Al, Ga, In). This gave us straightforward access to pincer-coordinated cations (2–7). These complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear magnetic resonance spectroscopy (1H, 13C, 29Si), high-resolution mass spectrometry techniques. Their electronic properties were further analyzed with help quantum chemical calculations.

Язык: Английский

Structural Snapshots of Reversible Carbon Dioxide Capture and (De)oxygenation at Group 14 Diradicaloids

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 8, 2024

Although diradicals should exhibit a rather small reaction barrier as compared to closed-shell species for activating kinetically inert molecules, the activation and functionalization of carbon dioxide with stable main-group remain virtually unexplored. In this work, we present thorough study on CO2 activation, reversible capture, (de)oxygenation mediated by Group 14 singlet (i.e., diradicaloids) [(ADC)E]2 (E = Si, Ge, Sn) based an anionic dicarbene (ADC) framework (ADC PhC{N(Dipp)C}2; Dipp 2,6-iPr2C6H3). readily undergo [4 + 2]-cycloadditions result in barrelene-type bis-metallylenes [(ADC)E]2(OC═O). The addition is E Ge; thus, detaches under vacuum or at elevated temperature regenerates [(ADC)Ge]2. [(ADC)Sn]2(OC═O) isolable but deoxygenates additional form [(ADC)Sn]2(O2CO) CO. [(ADC)Si]2(OC═O) extremely reactive could not be isolated detected it spontaneously reacts further yield elusive monomeric Si(IV) oxides [(ADC)Si(O)]2(COn) carbonates [(ADC)Si(CO3)]2(COn) (n 1 2) via CO2. molecular structures all compounds have been established X-ray diffraction, mechanistic insight their formation has suggested DFT calculations.

Язык: Английский

Redox Non-Innocent Bis-Silylene Aluminium Complexes with a Carborane Backbone

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

[AlI 2 + ] complexes of a bis-silylenyl carborane have been synthesised with three interconvertible ligand oxidation states. Further reduction using K(C 10 H 8 ) furnishes 1,4-naphthalene derivatives, indicative low state Al intermediates.

Язык: Английский