In the study of the metallic mercury interaction with cyclopalladated derivatives of tris-ortho-tolylphosphine [{(κ²P,C-L)Pd(μ-X)}₂], the redox-transmetallation of palladacycles by metallic mercury with the formation of P,C-chelated benzylmercurials [(κ²P,C-L)HgX] was revealed at moderate temperature in the presence of excess Hg(0). In contrast, the mercury(0) testing of the Suzuki reaction with the same chloride P,C-precatalyst gave a negative result, even at a higher temperature and with a greater excess of Hg(0). The structures of these mercurials have been convincingly confirmed spectrally (¹Н, ¹³С, ³¹Р and ¹⁹⁹Hg NMR), and via X-ray diffraction study and DFT calculations for the chloride mercurial. Our results and the analysis of known data on the mercury diagnostics of catalytic systems with classical and anomalous P,C-precatalysts enable us to assume that the intact state of palladacycle is present in the key anionic intermediate [(κ²P,C-L)Pd⁰]^– of catalytic cycles of the Suzuki and Heck reactions and a lower reactivity of Hg(0) with palladium(0) complexes in comparison with that of palladium(II) analogues.

在金属汞相互作用与三-环钯衍生物的研究邻-tolylphosphine [{（κ ² P，C -L）的Pd（μ-X）} ₂ ]，由与地层金属汞钯环的氧化还原金属转移的P，C -chelated benzylmercurials [（κ ² P，C -L）HGX]显露在过量汞（0）的存在下适度的温度。相反，即使在较高的温度下和过量的Hg（0）下，使用相同的氯化物P，C-预催化剂对Suzuki反应进行的汞（0）测试也给出了负面结果。这些汞的结构已经令人信服地证实光谱（¹ Н，¹³ С，³¹ Р和¹⁹⁹汞柱NMR），并通过用于氯乙烯水银X射线衍射研究和DFT计算。我们的研究结果和对与经典和反常催化体系的汞诊断已知数据的分析P，C -precatalysts使我们能够假定钯环的完整状态存在于关键阴离子中间体[（κ ² P，C -L ）Pd ⁰ ] ^– Suzuki和Heck反应的催化循环，与钯（II）类似物相比，Hg（0）与钯（0）配合物的反应性较低。