Zwitterionic 2-Phosphaethene-thiolates [(LC)P=CS(LC/P)]+ as PCS Building Blocks (LC = NHC, LP = PR3).

The zwitterionic compounds [(LC)P=CS(LC/P)]+ (3+, LC = NHC, LP = PR3), featuring cationic substituents at the phosphorus and carbon atoms, are synthesized as their triflate salts at a multi-gram scale from the reaction of Lewis base adducts of CS2, namely LC/P-CS2 (4), with a combination of [(LCP)4][OTf]4 (1[OTf]4) and Ph3P. The feasibility of using 3+ as PCS building blocks is showcased in their reactions with representative electrophiles (MeOTf) and nucleophiles (MesMgBr, Ph3PCH2), leading to selective functionalization of the PCS core at the S- and P-terminus, respectively. Additionally, it is reported that 3+ can function as ambident nucleophiles with AgOTf (2 equivalents), affording unprecedented linear coordination polymer [Ag2(OTf)3-μ2:κP,κS-((LC)P=CS(PCy3))]+ (6b), where the PCS moiety acts as a bridging ligand in transition metal complexes for the first time. Reduction of 3+ facilitates the cleavage of the P- and C-bound substituents leading to the formation of the [PCS]- anion. Moreover, cycloaddition reactions of 3+ with 1[OTf]4 are shown to selectively yield five- and eight-membered polyphosphorus heterocycles. Preliminary results suggest the possibility of activating the C-S bond in [(LC)P=CS(LC)]+, resulting in the formation of [(LC)P=C(LC)-P(LC)][OTf]2, 12[OTf]2, which may serve as a synthon for the PCP unit in future studies.