期刊
INORGANIC CHEMISTRY
卷 61, 期 27, 页码 10477-10485出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01325
关键词
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资金
- Welch Foundation [AX-1772]
- National Science Foundation [CHE-1625963, CHE-1920057]
This study employed iron-hydride and iron-boryl complexes to investigate the hydroboration of internal alkynes, revealing novel complexes as likely intermediates in the catalytic pathway.
Iron-hydride and iron-boryl complexes supported by a pyrrole-based pincer ligand, tBuPNP (PNP = anion of 2,5bis(di-tert-butylphosphinomethyl)pyrrole), were employed for a detailed mechanistic study on the hydroboration of internal alkynes. Several novel complexes were isolated and fully characterized, including iron-vinyl and iron-boryl species, which represent likely intermediates in the catalytic hydroboration pathway. In addition, the products of alkyne insertion into the Fe-B bond have been isolated and structurally characterized. Mechanistic studies of the hydroboration reaction favor a pathway involving an active iron-hydride species, [FeH(tBuPNP)], which readily inserts alkyne and undergoes subsequent reaction with hydroborane to generate product. The iron-boryl species, [Fe(BR2)(tBuPNP)] (R2 = pin or cat), was found to be chemically competent, although its use in catalysis entailed an induction period whereby the iron-hydride species was generated. Stoichiometric reactions and kinetic experiments were performed to paint a fuller picture of the mechanism of alkyne hydroboration, including pathways for catalyst deactivation and the influence of substrate bulk on catalytic efficacy.
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