The dinuclear cyclopalladated compounds [Pd2(μ-OAc)2(Ln)2] 2 derived from imines HLn = p-CnH2n + 1OC6H4CH NC6H4OCnH2n + 1-p1 (n = 2, 6 or 10) react with NaOH to give dinuclear derivatives [Pd2(μ-OH)2(Ln)2] 3. The reaction of 3 with amines (1 ∶ 1 molar ratio) yields the corresponding hydroxo–amido complexes [Pd2(μ-NHR)(μ-OH)(Ln)2] (R = CmH2m + 1 (m = 1, 6, 10, 14 or 18) 4 or C6H4C14H29-p5). With excess of amine [Pd2(μ-NHR)2(Ln)2] 6 (R = CmH2m + 1) are formed. Complexes 4 react with thiols or decanoic acid in 1 ∶ 1 mole ratio to give the corresponding amido–thiolato or amido–carboxylato complexes [Pd2(μ-SCjH2j + 1)(μ-NHR)(Ln)2] 7 ( j = 4, 10 or 18) or [Pd2(μ-O2CC9H19)(μ-NHR)(Ln)2] 8. The mononuclear complexes [Pd(S2CNR′2)(Ln)] (R′ = C2H59a or C8H179b) are prepared when complexes 3 are treated with dialkylamines in the presence of carbon disulfide. Most of the complexes show liquid crystal behaviour and nematic, smectic A and smectic C phases are found.
双核羰基
钯化合物 [Pd2(μ-OAc)2(Ln)2] 2 由
亚胺 HLn = p-CnH2n + 1OC6H4CH NC6H4OCnH2n + 1-p1 (n = 2, 6 或 10) 反应与 NaOH 生成双核衍
生物 [Pd2(μ-OH)2(Ln)2] 3。复合物 3 与胺反应(1 ∶ 1 摩尔比),生成相应的羟基-酰胺配合物 [Pd2(μ-NHR)(μ-OH)(Ln)2] (R = CmH2m + 1 (m = 1, 6, 10, 14 或 18) 4 或 C6H4C14H29-p5)。若胺过量,则形成 [Pd2(μ-NHR)2(Ln)2] 6 (R = CmH2m + 1)。复合物 4 与
硫醇或
癸酸以 1 ∶ 1 摩尔比反应,生成相应的酰胺-
硫代酸盐或酰胺-
羧酸盐配合物 [Pd2(μ-SCjH2j + 1)(μ-NHR)(Ln)2] 7 (j = 4, 10 或 18) 或 [Pd2(μ-O2CC9H19)(μ-NHR)(Ln)2] 8。当复合物 3 在二烷基胺和
二硫化碳的存在下处理时,制备单核配合物 [Pd(S2CNR′2)(Ln)] (R′ = C2H59a 或 C8H179b)。大多数复合物表现出液晶行为,发现有向列相、层状 A 相和层状 C 相。