REACTION OF METAL ION COMPLEXES WITH HYDROCARBONS .I. PALLADATION AND SOME OTHER NEW ELECTROPHILIC SUBSTITUTION REACTIONS . PREPARATION OF PALLADIUM(I)
REACTION OF METAL ION COMPLEXES WITH HYDROCARBONS .I. PALLADATION AND SOME OTHER NEW ELECTROPHILIC SUBSTITUTION REACTIONS . PREPARATION OF PALLADIUM(I)
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DOI：
10.1039/j19680001324
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发表时间：
1968-01-01
期刊：
影响因子：
--
通讯作者：
TRIGGS, C
中科院分区：
文献类型：
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作者：
DAVIDSON, JM;TRIGGS, C
本文对能取代苯中氢离子形成芳金属配合物的金属离子进行了研究。某些稳定的复合物被分离出来，而热不稳定的复合物的形成被检测到的联苯的外观。同位素示踪法被用来寻找水解不稳定的配合物。金（III）、汞（II）和铊（III）在酸水溶液中与苯反应，而金（III）、汞（II）、钯（II）、铂（II）和铊（III）在乙酸溶液中反应。反应性与“B类”字符相关。本文研究了二乙酸钯与苯和甲苯在0.5N高氯酸的乙酸溶液中的反应。这似乎是一个亲电取代，产生芳基钯配合物。这些化合物通过协同机制分解，根据温度产生联芳基化合物和钯金属或单价钯络合物。分离出一种爆炸性紫色配合物[Pd（C6 H6）（H2O）ClO 4]n。在高氯酸-乙酸中，苯与二乙酸合钯于50° C反应时，用该化合物在380和550 mµ处的紫外吸收测定其在溶液中的出现速率。动力学数据与苯与单体钯（II）之间的二级反应（k ~ 2 = 4·6 × 10 ~（-4）l·mol ~（-1）sec ~（-1））和随后的快速分解一致。对于氘代苯，发现了大的原生同位素效应（kH/kD= 5.0）。
A survey has been made to identify those metal ions that will displace hydrogen ions from benzene with formation of arylmetal complexes. Certain stable complexes were isolated while the formation of thermally unstable complexes was detected by the appearance of biphenyl. An isotopic tracer method was used to seek hydrolytically unstable complexes. Gold(III), mercury(II), and thallium(III) react with benzene in aqueous acid solution while gold(III), mercury(II), palladium(II), platinum(II), and thallium(III) react in acetic acid solution. Reactivity is associated with ‘class b’ character. A more detailed study of the reaction of diacetatopalladium with benzene and toluene in 0·5N-perchloric acid in acetic acid was made. It appears to be an electrophilic substitution that yields arylpalladium complexes. These decompose by a concerted mechanism to give biaryls and either palladium metal or a univalent palladium complex depending on temperature. An explosive purple complex, [Pd(C6H6)(H2O)ClO4]n has been isolated. The ultraviolet absorption of this compound at 380 and 550 mµ has been used to determine its rate of appearance in solution during the reaction of benzene with diacetato-palladium in perchloric acid–acetic acid at 50°. The kinetic data are consistent with a second-order reaction between benzene and monomeric palladium(II)(k2= 4·6 × 10–4l.mole–1sec.–1) followed by fast decomposition. For deuteriobenzene, a large primary isotope effect (kH/kD= 5·0) was found.