Carbonyl sulfide (COS) is an air pollutant that causes acid rain, ozonosphere damage, and carbon dioxide (CO) generation. It is a heterocumulene and structural analogue of CO. Relevant to organic synthesis, it is a source of C═O or C═S groups and thus an ideal one-carbon (C1) building block for synthesizing sulfur-containing polymers through the similar route of CO copolymerization. In contrast, traditional synthesis of sulfur-containing polymers often involves the condensation of thiols with phosgene and ring-opening polymerization of cyclic thiocarbonates that are generally derived from thiols and phosgene; thus, COS/epoxide copolymerization is a "greener" route to supplement or supplant current processes for the production of sulfur-containing polymers. This Accounts highlights our efforts on the discovery of the selective formation of poly(monothiocarbonate)s from COS with epoxides via heterogeneous zinc-cobalt double metal cyanide complex (Zn-Co(III) DMCC) and homogeneous (salen)CrX complexes. The catalytic activity and selectivity of Zn-Co(III) DMCC for COS/epoxide copolymerization are similar to those for CO/epoxide copolymerization. (salen)CrX complexes accompanied by onium salts exhibited high activity and selectivity for COS/epoxide copolymerization under mild conditions, affording copolymers with >99% monothiocarbonate units and high tail-to-head content up to 99%. By way of contrast, these catalysts often show moderate or low activity for CO/epoxide copolymerization. Of note, a specialty of COS/epoxide copolymerization is the occurrence of an oxygen-sulfur exchange reaction (O/S ER), which may produce carbonate and dithiocarbonate units. O/S ER, which are induced by the metal-OH bond regenerated by chain transfer reactions, can be kinetically inhibited by changing the reaction conditions. We provide a thorough mechanistic understanding of the electronic/steric effect of the catalysts on the regioselectivity of COS copolymerization. The regioselectivity of the copolymerization originates from the solely nucleophilic attack of the sulfur anion to methylene of the epoxide, and thus, the chiral configuration of the monosubstituted epoxides is retained. COS-based copolymers are highly transparent sulfur-containing polymers with excellent optical properties, such as high refractive index and Abbe number. Thanks to their good solubility and many available epoxides, COS/epoxide copolymers can potentially be a new applicable optical material. Very recently, crystalline COS-based polymers with or without chiral carbons have been synthesized, which may further expand the scope of application of these new materials.

We report the first example of a regioregular and fully alternating poly (propylene monothiocarbonate) (PPMTC) from the well-controlled copolymerization of two asymmetric monomers, carbonyl sulfide and racemic propylene oxide, using (Salen)CrCl in conjunction with bis(triphenylphosphoranylidene)ammonium chloride. The maximum turnover of frequency of this catalyst system was 332 h −1 at 25°C. The contents of monothiocarbonate and tail-to-head linkages of PPMTC were up to 100% (based on 1 H NMR spectra) and 99.0% (based on 13 C NMR spectra), respectively. PPMTC samples have number-average molecular weight (M n ) up to 25.3 kg/mol with polydispersity index of 1.41. The very low decomposition temperature of 137°C and high refractive index of 1.63 of PPMTC make it a potential scarifying optical adhesive.

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The catalytic coupling of oxetane, the symmetric isomer of propylene oxide, with carbon disulfide has been investigated utilizing (salen)CrCl in the presence of various onium salts. Oxygen and sulfur atom exchange was observed in both the polymeric and cyclic carbonate products. The coupling of oxetane and CS 2 was selective for copolymer formation over a wide range of reaction conditions. Five different polymer linkages and two cyclic products were determined by 1 H and 13 C NMR spectroscopy, and these results were consistent with in situ infrared spectroscopic monitoring of the process. The major cyclic product produced in the coupling process was trimethylene trithiocarbonate, which was isolated and characterized by single crystal X-ray crystallography. Upon increasing the CS 2 /oxetane feed ratio, a decrease in the O/S scrambling occurred. The reaction temperature had the most significant effect on the O/S exchange process, increasing exchange with increasing temperature. The presence of the onium salt initiator both accelerated the coupling process and promoted O/S scrambling. COS (observed), and CO 2 intermediates are proposed in the reactions leading to various polymeric linkages.