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Updated: May 23, 2026

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Titanium(IV) complexes of disulfide-linked Schiff bases
Alberto Donzelli1, Imir Metushi, Pierre G Potvin
1Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario, Canada M3J 1P3.
Abstract:
With the goal of preparing Ti(IV) complexes bearing a sulfur-based redox function of possible use in electrocatalytic oxidations of alcohols at electrode surfaces, a series of seven 2,2'-dithiodianiline Schiff-base derivatives, including two new variations, were tested in reactions with Ti(OR)(4) (R = (i)Pr, (t)Bu). Instead of the expected dimetallic products of general formula [LTi(OR)(2)](2), mononuclear species LTi(OR)(2) were obtained, confirmed by crystallographic determinations to have an unprecedented, symmetrical, and macrocyclic arrangement with four-point binding to the metal center and with the disulfide moieties remaining uncoordinated. Cyclic voltammetry performed in CH(2)Cl(2) displayed oxidations at potentials useful for fuel cells (+1.1-1.5 V vs Ag/AgCl), but despite the uncoordinated disulfide moieties, the complexes were reticent to engage in reduction processes.
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