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引用次数: 0
摘要
在三烷基硼烷与 CO 的羰基化反应中,所有三个烷基都发生了从 B 到 C 的逐步迁移插入,但除了第一个烷基迁移产生了酰基硼烷之外,这一经典的简单图景并不正确。由于贫电子 B 原子中的 B-C 键不活化,第二和第三个直接烷基转移在动力学上受到阻碍。后者只能通过最终烷基硼氧化物的自催化作用或通过在硼酸盐中心形成B-烷基键被削弱的二聚物来实现。热力学参数和一些与核色谱分析有关的参数都表明,烷基硼氧化物的最终环三聚产物硼氧烷的芳香性质很少,甚至是 "负 "的。
The classical simple picture of stepwise B-to-C migratory insertion of all three alkyl groups in the carbonylation reaction of trialkyl boranes with CO was shown not to be correct, except for the first alkyl group shift affording an acyl borane. The second and third direct alkyl shifts turned out to be kinetically hampered due to the non-activated character of the B−C bond in electron-poor B atoms. The latter can only be achieved by either the autocatalytic action of the final alkyl boron oxide or by formation of dimeric species with weakened B-alkyl bonds at borate centres. Both thermodynamic and several NICS-related parameters pointed to scarce, even “negative”, aromatic character for boroxines, the final cyclotrimerization products of alkyl-boron oxides.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.