Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene.: Generation and experimental discrimination of hypotheses
Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene.: Generation and experimental discrimination of hypotheses
复制标题
DOI：
10.1007/bf02494629
复制
发表时间：
1999-05-01
影响因子：
1.7
通讯作者：
Temkin, ON
中科院分区：
文献类型：
--
作者：
Bruk, LG;Gorodski, SN;Temkin, ON
采用正式和非正式的方法对PdCl2-CuCl-CuCl2体系催化苯乙炔氧化羰基化制苯丙酸甲酯的反应机理进行了假设。经过鉴别和所有实验数据一致的假设包括Cu-I炔基配合物的形成步骤，苯乙基从Cu-I转移到Pd-II，一氧化碳插入Pd-II sigma-炔基配合物的Pd-C或Pd-OMe键。通过对正式和非正式两种提出假设方法的比较，证实了第一种方法的效率更高。
Formal and informal methods for advancing hypotheses on mechanisms were used in a study of the oxidative carbonylation of phenylacetylene to methyl phenylpropiolate catalyzed by the PdCl2-CuCl-CuCl2 system. The hypotheses remaining after discrimination and consistent with all experimental data include the steps of formation of the Cu-I alkynyl complex, transfer of the phenylethynyl group from Cu-I to Pd-II, insertion of carbon monoxide into a Pd-C or Pd-OMe bond of the Pd-II sigma-alkynyl complex. Comparison of the formal and informal methods for advancing hypotheses confirmed a higher efficiency of the first method.