Piperazine‐Derived Heteroleptic Cd(II) Silanethiolates: Structural Insights, Catalytic Activity in Allyl Alcohol Oligomerization, and CO₂ Sorption Properties

ABSTRACT Three new complexes—mononuclear [Cd{SSi (O t Bu) 3 } 2 (amppz)] 2 ⋅6CH 3 OH 1 , binuclear [( μ ‐amppz)[Cd{SSi (O t Bu) 3 }][{Cd{SSi (O t Bu) 3 } 2 ·CH 3 OH}] 2 , and polynuclear [Cd{SSi (O t Bu) 3 } 2 ( μ ‐ppz)] n 3 —have been obtained in the reaction of piperazine (ppz) and 1‐(2‐aminoethyl)piperazine (amppz) with [Cd{SSi (O t Bu) 3 } 2 ] 2 in diverse molar ratios of the reagents. Characterization of the properties of the obtained compounds was performed using a broad range of techniques: single‐crystal X‐ray diffraction, FTIR and UV–Vis spectroscopy, TG, and DSC analysis. Theoretical calculations were performed using density functional theory (DFT) to optimize molecular geometries, complemented by noncovalent interaction (NCI) analysis to map key intermolecular forces. IR and UV–Vis spectra were also simulated to support the experimental characterization. Luminescence studies have shown that crystalline 1 – 3 exhibit dual emission at room temperature ascribed to the intraligand transition. Compound 1 was further investigated for potential CO 2 sorption and initiation of allyl alcohol oligomerization in the presence of MAO as the activator of the process. To date, the use of any cadmium(II) compounds in the polymerization of allyl alcohol has not been described in the literature.