Reaction of the palladium(II) and platinum(II) isocyanide complexes cis-[MCl₂(CNR)₂] [M = Pd, R = C₆H₃(2,6-Me₂) (Xyl), 2-Cl-6-MeC₆H₃, cyclohexyl (Cy), t-Bu, C(Me)₂CH₂(Me)₃ (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC₆H₃, Cy, t-Bu, and tmbu] with N,N′-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated monocarbene monochelated species, while the next addition grants the deprotonated bis-carbene bis-chelated metal compounds. DPG behaves as nucleophile, deprotonating base, and chelator. The addition of DPG proceeded with different regioselectivity depending on the metal center and, in a larger extent, on the substituent R in RNCs. The X-ray diffraction studies for the deprotonated mono- and bis-carbene complexes confirmed the regioisomerism of these species and allowed the identification of ADC protolytic forms stabilized in the solid-state. 1D (¹H and ¹³C{¹H}) and 2D (¹H,¹H-NOESY; ¹H,¹⁵N-HSQC; ¹H,¹⁵N-HMBC) solution NMR of the obtained systems demonstrated their configuration isomerism accompanied by prototropic tautomerism. Together, the solid-state and solution data provide an insight into the flexible character of ADC species.

中文翻译：

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N，N'-^二苯基胍与金属活化的异氰酸酯加成后形成的氨基卡宾Pd ^II和Pt ^II配合物中异构化模式和蛋白水解形式的多样性

钯（II）和铂（II）异氰化物配合物的反应顺式-[MCl ₂（CNR）₂ ] [M = Pd，R = C ₆ H ₃（2,6-Me ₂）（Xyl），2-Cl -6-MeC ₆ H ₃，环己基（Cy），t- Bu，C（Me）₂ CH ₂（Me）₃（1,1,3,3-四甲基丁-1-基缩写为tmbu）；M = Pt，R = Xyl，2-Cl-6-MeC ₆ H ₃，Cy，t- Bu和tmbu]，其中N，N'-二苯基胍（DPG）导致DPG衍生的金属结合的去质子化的无环二氨基卡宾（ADC）物种。该反应通过两步过程进行，包括将胍与一种异氰酸酯进行初始偶联，并导致去质子化的单卡宾单螯合物质，而下一次添加则得到去质子化的双卡宾双螯合金属化合物。DPG表现为亲核试剂，去质子化碱基和螯合剂。DPG的添加以不同的区域选择性进行，这取决于金属中心，并且在更大程度上取决于RNC中的取代基R。对去质子化的单-和双-卡宾配合物的X射线衍射研究证实了这些物种的区域异构现象，并允许鉴定稳定在固态的ADC蛋白质水解形式。1D（¹ H和所得系统的¹³ C { ¹ H}）和2D（¹ H，¹ H-NOESY；¹ H，¹⁵ N-HSQC；¹ H，¹⁵ N-HMBC）溶液NMR证实了它们的构型异构现象伴随质子互变异构现象。固态数据和解决方案数据一起提供了对ADC种类的灵活特性的深入了解。