Catalysts are employed in chemical reactions ranging from relatively simple small molecule transformations to polymerization and crosslinking for immediate application use. In the latter case, the catalyst, typically a reactive metal species, remains entrained in the polymer network in its active form. This can potentially lead to future network degradation due to the reactive nature of the catalyst. Deactivation of the active species post-catalysis through an external stimulus, such as heat, friction, or light, offers a possibility to mitigate this issue. The polydentate disulfide ligand, 1,2-bis(pyridin-2-ylmethyl)disulfane, was prepared in pursuit of a ligand scaffold with a deactivatable backbone (i.e. the disulfide). This ligand was reacted with a series of metal halides producing mononuclear complexes with varying geometric configurations. The metal complexes were investigated using X-ray crystallography and spectroscopy where available. Complexes with zinc(II) and copper(I) adopt tetrahedral geometries, while copper(II) and cobalt(II) adopt trigonal bipyramidal geometries. While both trigonal bipyramidal, the axial positions for the copper(II) and cobalt(II) structures differ. Several solvate and one kryptoracemate crystal structures were obtained. Curiously, no reaction was observed between the ligand and iron(II), iron(III), cobalt(III), or nickel(II) halides.

Reactivity between late first-row transition metal halides and the ligand 1,2-bis(pyridin-2-ylmethyl)disulfane: Vibrantly-colored complexes and their crystal structures

ACS Spring 2022

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