Caise Alexa, Griffin Liam P, McManus Caitilín, Heilmann Andreas, Aldridge Simon
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202117496. doi: 10.1002/anie.202117496. Epub 2022 Feb 26.
We report on the reversible uptake of carbon dioxide by dimetallynes featuring ancillary hemi-labile pincer ligands. Insertion into the Ge-Ge/Sn-Sn bonds yields species containing an E(CO )E unit, with the mode of ligation of the CO fragment determined crystallographically being found to be dependent on the identity of the Group 14 element. The thermodynamics of CO uptake/loss can be established through VT NMR (ΔH°=+24.6(2.3) kJ mol , ΔS°=+64.9(3.8) J mol K , ΔG° =+5.3(1.9) kJ mol for the loss of CO in the Ge case), and the chemical consequences of reversibility demonstrated by thermodynamically-controlled exchange reactions.
我们报道了具有辅助半不稳定钳形配体的双金属炔对二氧化碳的可逆吸收。插入Ge-Ge/Sn-Sn键会生成含有E(CO)E单元的物种，通过晶体学确定的CO片段的连接模式被发现取决于第14族元素的身份。CO吸收/释放的热力学可以通过变温核磁共振确定（对于Ge的情况，CO释放时ΔH°=+24.6(2.3) kJ·mol⁻¹，ΔS°=+64.9(3.8) J·mol⁻¹·K⁻¹，ΔG° =+5.3(1.9) kJ·mol⁻¹），并且通过热力学控制的交换反应证明了可逆性的化学后果。
