Carbon Monoxide Release from Aryl-Propargyl Dicobalt(0)Hexacarbonyl Derivatives: A Computational and Experimental Study

In the present study, wefocusondinuclearcobalt-basedCO-RMswiththeaimofelucidating their CO release mechanism, as well as to understand how structural changes targeted to modify the electronic properties of these compounds can modulate CO delivery. To this end, we specifically synthesized a set of phenyl-propargyl-based CO-RMs bearing–NO2,–H, and–OCH3 as para substituents (R) with varying mesomeric influence (M) and different heteroatoms (X = NH, O, or S) linking the propargyl tail and the aromatic ring. The effects of R and X in modulating CO release were assessed by using several experimental and computational techniques to obtain a coherent picture and to shed light on the stability and release properties of Co-based CO-RMs.