Cationic η3-allyl complexes. 21. Telomerization of buta-1,3-diene with Z–H compounds mediated by group 10 complexes
作者:Faouzi Bouachir、Pierre Grenouillet、Denis Neibecker、Jacques Poirier、Igor Tkatchenko
DOI:10.1016/s0022-328x(98)00789-x
日期:1998.10
, where Y− is a non-coordinating anion (BF4−, ClO4−, BF4−) have been examined in telomerization reactions of buta-1,3-diene with representative nucleophiles. No reaction are observed for nickel complexes, due to their high reactivity versus nucleophiles. With palladium complexes, the reaction only occurs with alcohols and provides an increased selectivity for telomers with more than two diene units
阳离子(η 3 -烯丙基)通式的配合物[(η 3 -烯丙基)M(配体)2 ] + ÿ - ,其中Y -是一个非配位阴离子(BF 4 -,CLO 4 -,BF 4 - )已在buta-1,3-diene与代表性亲核试剂的端粒化反应中进行了研究。由于镍配合物相对于亲核试剂的反应性高,因此未观察到任何反应。对于钯配合物,该反应仅与醇发生,并且对于具有两个以上二烯单元的端粒提供更高的选择性,从而导致C 16,C 24甚至更高的醚。尽管反应活性低得多,但是当使用氢硅烷时,铂络合物也可以产生更高的端粒。提出至少在钯的情况下,C 16和C 24醚的形成是由于二聚钯中间体中的C 8单元与作为桥连配体的调质子的偶联而引起的。