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.

中文翻译：

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两性离子 2-磷酸烯硫醇酯 [（LC）P=CS（LC/P）]+ 作为 PCS 构建单元 （LC = NHC， LP = PR3）


两性离子化合物 [（LC）P=CS（LC/P）]+ （3+， LC = NHC， LP = PR3），在磷和碳原子处具有阳离子取代基，由 CS2 的路易斯碱加合物反应合成为多克级的三氟甲磺酸盐，即 LC/P–CS2 （4），由 [（LCP）4][OTf]4 （1[OTf]4） 和 Ph3P 组合而成。使用 3+ 作为 PCS 构建单元的可行性在它们与代表性亲电试剂 （MeOTf） 和亲核试剂 （MesMgBr， Ph3PCH2） 的反应中得到证明，导致 PCS 核心分别在 S 端和 P 端选择性功能化。此外，据报道，3+ 可以与 AgOTf（2 个当量）一起作为亲核试剂发挥作用，提供前所未有的线性配位聚合物 [Ag2（OTf）3‐μ2：κP，κS–（（LC）P=CS（PCy3））]+ （6b），其中 PCS 部分首次在过渡金属配合物中充当桥接配体。3+ 的还原促进了 P 和 C 结合的取代基的裂解，从而形成 [PCS] – 阴离子。此外，3+ 与 1[OTf]4 的环加成反应显示选择性地产生五元和八元多元多磷杂环。初步结果表明，有可能在 [（LC）P=CS（LC）]+ 中激活 C-S 键，导致形成 [（LC）P=C（LC）–P（LC）][OTf]2， 12[OTf]2，在未来的研究中可能作为 PCP 单元的合成子。