An oxophosphoryl-substituted methanide ligand system for transition metal complexes has been synthesized and isolated as the sodium salt Na[Ph₂P(O)–C(H)–SO₂Ph]. This ligand features structural components known to enable the isolation of nucleophilic late transition metal carbene complexes. The corresponding ruthenium(cymene) chlorido complex was readily available by simple salt metathesis reaction. However, in contrast to previously reported thio- and iminophosphoryl-tethered ligand systems, dehydrohalogenation of the chlorido complex led to the formation of a cyclometallated ruthenium complex instead of the carbene complex. All compounds have been characterized in solution and solid state. Additional density functional theory (DFT) studies have been performed to elucidate the mechanism of the observed cyclometallation and to shed light on the effects of different P(V) groups in the ligand system on the stability and reactivity of the corresponding carbene complexes. The calculations show that the weaker coordination of the PO compared to the PS or PN moiety is responsible for the more facile C–H activation.

已合成并分离了用于过渡金属配合物的氧代磷酰基取代的甲烷化物配体系统，作为钠盐Na [Ph ₂ P（O）–C（H）–SO ₂Ph]。该配体具有已知能够分离亲核后期过渡金属卡宾配合物的结构成分。可以通过简单的盐复分解反应容易地获得相应的钌（苏木）氯离子络合物。然而，与先前报道的硫代和亚氨基磷酰基系的配体系统相反，氯配合物的脱卤化氢导致形成环金属化钌配合物而不是卡宾配合物。所有化合物均以溶液和固态表征。已经进行了其他密度泛函理论（DFT）研究，以阐明观察到的环金属化的机理，并阐明配体系统中不同P（V）基团对相应卡宾配合物的稳定性和反应性的影响。与PS或P N部分相比，O负责更轻松的CH活化。