Syntheses of .eta.5-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on carbon monoxide substitution reactions
Syntheses of .eta.5-heterocyclic manganese tricarbonyls. Effect of the heteroatom and heterocycle ring substituents on carbon monoxide substitution reactions
复制标题
η5-杂环三羰基锰的合成。
DOI：
10.1021/ja00258a024
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发表时间：
1987
影响因子：
15
通讯作者：
F. Basolo
中科院分区：
文献类型：
--
作者：
D. L. Kershner;F. Basolo
报道了几种新型η/sup 5/-杂环三羰基锰配合物的合成与表征。动力学研究这些氮族η/sup 5/-二甲基杂环锰三羰基配合物的CO取代反应的报告。结果表明，含磷亲核试剂仅对含氮杂环化合物进行CO取代。这些结果归因于N的电负性大于C、P或As的电负性。三羰基（η/sup 5/-3，4-二甲基吡咯基）锰（I）和三羰基（η/sup 5/-2，5-二甲基吡咯基）锰（I）均通过缔合途径取代CO，其中反应速率与金属络合物浓度成一级关系，与进入的亲核试剂浓度成一级关系。前一种化合物还通过独立于进入的亲核试剂浓度的途径取代CO。二级途径被认为涉及环滑移（eta/sup 5/.. -->. eta/sup 3/.. -->..η/sup 5/）机制，而一级途径似乎涉及配体解离机制。
The synthesis and characterizations of some new eta/sup 5/-heterocyclic manganese tricarbonyl complexes are described. Kinetic studies are reported for CO substitution reactions of these nitrogen family eta/sup 5/-dimethylheterocyclic manganese tricarbonyl complexes. The results show that only the N-heterocycle compounds undergo CO substitution by phosphorus nucleophiles. These results are attributed to the greater electronegativity of N than that of C, P, or As. Both tricarbonyl(eta/sup 5/-3,4-dimethylpyrrolyl)manganese(I) and tricarbonyl(eta/sup 5/-2,5-dimethylpyrrolyl)manganese(I) substitute CO by an associative pathway in which the reaction rates are first order in concentration of metal complex and first order in concentration of entering nucleophile. The former compound also substitutes CO by a pathway that is independent of the concentration of incoming nucleophile. The second-order pathway is believed to involve a ring-slippage (eta/sup 5/ ..-->.. eta/sup 3/ ..-->.. eta/sup 5/) mechanism, whereas the first order pathway appears to involve a ligand-dissociation mechanism.