Palladium(<scp>II</scp>) complexes derived from the potentially chelating ligands 2,2,NN-tetramethylpent-4-enylamine and 2,2-dimethylpent-4-enyl methyl sulphide. Crystal structures of dichloro[2,2-dimethylpent-(E)-3-enyl methyl sulphide]palladium(<scp>II</scp>) and chloro[1–3-η-syn-1-(1,1′-dimethyl-2′-methylthioethyl)allyl]palladium(<scp>II</scp>)
作者:Robert McCrindle、Elmer C. Alyea、George Ferguson、Shelton A. Dias、Alan J. McAlees、Masood Parvez
DOI:10.1039/dt9800000137
日期:——
Reaction of PdX2·2PhCN(X = Cl or Br) with 2,2,NN-tetramethylpent-4-enylamine (1a) gives complexes (2) of stoicheiometry PdX2·(1a) in which Pd–X has added to the olefinic bond to generate a seven-membered chelate ring. In contrast, 2,2-dimethylpent-4-enyl methyl sulphide (1b) initally gives labile olefinic complexes, which readily rearrange to the derivatives (5a) and (5b) of 2,2-dimethylpent-(E)-3-enyl
PDX的反应2 ·2PhCN(X = Cl或Br)与2,2,NN -tetramethylpent -4-烯基胺(1a)中给出的stoicheiometry(2)配合物PDX 2 ·(1a)中,其中已经PDX加入到烯烃键生成七元螯合环。相反,2,2-二甲基戊-4-烯基甲基硫醚(1b)最初产生不稳定的烯烃络合物,该化合物容易重新排列为2,2-二甲基戊-(E)-3-烯基的衍生物(5a)和(5b)甲基硫化物(13)。恒温1H nmr研究表明,在低温下(5a)和(5b)在溶液中以硫的形式存在一对差向异构体,而加热首先导致差向异构体平衡,然后导致金属-烯烃键失活。由(5a)和(5b)制备了π-烯丙基物质(6a)和(6b)。报告了(5a)和(6a)的X射线结构。的(5a)的晶体是单斜晶系,空间群P 2 1 / Ñ与Ž = 4在尺寸上的单元电池一个= 8.365(2),b = 15.068(2),C ^