An Iron‐Hydrogen Bond Resistant to Protonation and Oxidation

An Iron‐Hydrogen Bond Resistant to Protonation and Oxidation
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抗质子化和氧化的铁氢键

DOI:
10.1002/zaac.202100066
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发表时间:
2021
期刊:
Zeitschrift für anorganische und allgemeine Chemie
影响因子:
--
通讯作者:
Guan, Hairong
Guan, Hairong
中科院分区:
--
文献类型:
--
作者:
Collett, Joel D.;Ransohoff, Rebecca W.;Krause, Jeanette A.;Guan, Hairong

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A new synthetic route tocis‐(CyPNP)Fe(CO)2H (CyPNP=2,5‐bis(dicyclohexylphosphinomethyl)pyrrolyl) has been developed, involving the reaction of (CyPNP)Fe(CO)2Br with NaBH4. The Fe−H bond of this iron hydride is remarkably stable to acids (e. g., HBF4⋅ Et2O, HCl, and CH3CO2H) and oxidants (e. g., 1,4‐benzoquinone and galvinoxyl), only leading to the protonation of the β‐pyrrolic carbon and the oxidation of the ligand backbone, respectively. Under 369 nm UV irradiation,cis‐(CyPNP)Fe(CO)2H has been shown to react with ethylene to yieldcis‐(CyPNP)Fe(CO)2Et and undergo H/D exchange with C6D6to formcis‐(CyPNP)Fe(CO)2D and C6D5H. Both processes likely proceed via an initial CO dissociation step to yield (CyPNP)Fe(CO)H as a reactive intermediate.
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