Treatment of the Schiff base ligands a–f with Li₂[PdCl₄]/NaAcO in methanol under reflux gave the single nuclear palladacycles 1a–1f, with the metal atom bonded to a terdentate monoanionic [C,N,S] iminic ligand and to a chloride ligand that completes the palladium coordination sphere. Reaction of 1a–1c with silver perchlorate/triphenylphosphine in acetone at room temperature yielded the single nuclear complexes 2a–2c as the perchlorate salts, after substitution of the chloride ligand by a triphenylphosphine. However, reaction of a–c with Na₂[PdCl₄]/NaAcO in methanol at room temperature also gave compounds 1a–1c albeit contaminated with small amounts of the corresponding free aldehyde (mixture A). Reaction of mixture A with silver perchlorate/triphenylphosphine in acetone at room temperature gave analogously 2a–2c with some of the corresponding free aldehyde (mixture B). Attempts to purify mixtures A and B via recrystallization produced single crystals of 5 and 6 respectively: two serendipitously formed complexes, bearing thiomethyl aniline and/or acetate ligands, and void of aldehyde or iminic residue; the structures contain eight- and six-membered rings of alternating palladium and nitrogen atoms, respectively. To clarify this situation the aniline itself was reacted with palladium(II) acetate or with Na₂[PdCl₄]; in the latter case after recrystallization a unique behavior is revealed, giving rise to a tetranuclear complex containing a Pd₄N₄ ring with three differing coordination environments on the palladium atoms. Treatment of 1d with Ph₂PCH₂PPh₂ (dppm)/AgClO₄ or with Ph₂PCH₂(PPh₂)W(CO)₅/AgClO₄ gave 3d, with a mono-coordinated dppm ligand, and 4d, respectively; complex 3d could not be converted into 4d by reaction with W(CO)₅(THF). Recrystallization of 4d gave a still further noticeable species, complex 8: a pentanuclear trans-configured heterometallic mixed valent Pd(II)/W(0) linear complex with the palladium atoms supported by two acetate and two thiomethyl aniline bridging ligands. The complexes were fully characterized by microanalysis, IR, ¹H, and ³¹P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 1b, 5, 6, 7 and 8 are described.

中文翻译：

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席夫碱-[C,N,S]钳状钯环的反应性：水解产生单一三核、四核和异五核 Pd3W2 配位配合物

在甲醇中回流下用 Li ₂ [PdCl ₄ ]/NaAcO处理席夫碱配体a–f得到单核环钯1a–1f，其中金属原子与三齿单阴离子 [C,N,S] 亚胺配体键合，并且形成完成钯配位层的氯化物配体。1a-1c与高氯酸银/三苯基膦在丙酮中在室温下反应，在氯配体被三苯基膦取代后，生成高氯酸盐形式的单核配合物2a-2c 。然而， a–c与 Na ₂ [PdCl ₄ ]/NaAcO 在甲醇中在室温下反应也得到化合物1a–1c，尽管被少量相应的游离醛污染（混合物 A）。混合物 A 与高氯酸银/三苯基膦在丙酮中在室温下反应，类似地得到2a-2c以及一些相应的游离醛（混合物 B）。尝试通过重结晶纯化混合物A和B，分别产生5和6的单晶：两种偶然形成的络合物，带有硫甲基苯胺和/或乙酸酯配体，并且不含醛或亚胺残基；该结构分别包含交替的钯和氮原子的八元环和六元环。为了澄清这种情况，苯胺本身与乙酸钯( II )或Na ₂ [PdCl ₄ ]反应；在后一种情况下，重结晶后会显示出独特的行为，产生含有钯原子上具有三种不同配位环境的 Pd ₄ N ₄环的四核络合物。用Ph ₂ PCH ₂ PPh ₂ (dppm)/AgClO ₄或用Ph ₂ PCH ₂ (PPh ₂ )W(CO) ₅ /AgClO ₄处理1d分别得到具有单配位dppm配体的3d和4d；配合物3d不能通过与 W(CO) ₅ (THF)反应转化为4d 。 4d的重结晶给出了更值得注意的物质，络合物8：五核反式构型异金属混合价 Pd( II)/W(0) 线性配合物，其中钯原子由两个乙酸酯和两个硫甲基苯胺桥配体支撑。根据需要，通过微量分析、IR、 ¹ H 和³¹ P NMR 光谱对复合物进行了充分表征。描述了化合物1b、5、6、7和8的X射线单晶分析。