With the LCr AM in hand, we turned towards the ROCOPs of CO2 and CS2 with the commonly employed benchmark epoxide cyclohexene oxide (CHO) (ESI Section S3 and S4). CO2/CHO ROCOP was performed at a loading of 1 eq. LM AM to 1000 eq. CHO, 100°C, 4 bar CO2 pressure, and monitored by aliquot analysis via 1 H NMR to accurately compare reaction kinetics and product distributions. In doing so we found an increase in selectivity and activity when moving to heavier alkali metals (LCr Cs ≈ LCr K ≈ LCr Rb > LCr Na > LCr , with LCr Cs > LCr K ) with TOFs ranging from 30 -157 h -1 (Table , run #1-5). All catalysts exhibit excellent polymer (i.e. < 5% c5c production) and linkage selectivity (i.e. > 99% carbonate versus ether links) except for LCr producing approximately 24% ether linkages resulting from epoxide homopropagation. The copolymerisations yield materials with bimodal molecular weights (Mn = 6.26 -14.41 kDa, Đ = 1.24 -1.46) increasing with monomer conversions typically observed in CO2/CHO ROCOP. Increasing the reaction temperature results in higher TOFs of 443 h -1 at 120°C and slightly decreases the polymer selectivity vs. c5c (Figure ) to 92% (63% polymer selectivity at 140°C) due to entropically favoured c5c generation. Having established LCr AM as active catalysts we moved towards exploring CS2/CHO ROCOP which was conducted at 60°C at a loading of 1 eq. LCr AM : 1000 eq. CHO : 2000 eq. CS2. As can be seen in the NMR spectrum in Figure , significantly more complex product mixtures are produced. In addition to the expected polymer comprising dithiocarbonate R-O-C(=S)-S-R (OSS, (C q =S) = 212.2 ppm) links from formal alternating CS2 and CHO insertion, one also observes the monothiocarbonate R-O-C(=O)-S-R (OOS, (C q =O) = 169.1 ppm) and R-O-C(=S)-O-R (OSO, (C q =S) = 193.2 ppm) links as well as the trithiocarbonate R-S-C(=S)-S-R (SSS, (C q =S) = 220.6 ppm) and carbonate R-O-C(=O)-O-R (OOO, (C q =S) = 153.9 ppm) links, which we could further evidence by FTIR spectroscopy of the isolated polymer (Figure ). Apart from polymeric (thio)carbonates one also observes the formation of cyclohexene sulfide (CHS) and "unscrambled" dt-c5c as the only cyclic carbonate byproduct (Figure ). Pol.