Synthesis of Bis(trityl)iron(II) and Formation of the Iron(0)-Stabilized o , o -Isomer of Gomberg’s Dimer

Synthesis of Bis(trityl)iron(II) and Formation of the Iron(0)-Stabilized o , o -Isomer of Gomberg’s Dimer
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双(三苯甲基)铁(II)的合成和铁(0)稳定的Gomberg二聚体的o,o-异构体的形成

DOI:
10.1021/acs.organomet.1c00616
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发表时间:
2021
期刊:
影响因子:
2.8
通讯作者:
Hayton, Trevor W.
Hayton, Trevor W.
中科院分区:
化学2区
文献类型:
--
作者:
Touchton, Alexander J.;Wu, Guang;Hayton, Trevor W.

文献摘要

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在-25 °C下,用2当量的Li(CPh 3)在THF中处理Fe(OAc)2导致以22%的产率形成[Fe(η5-CPh 3)2](1)。配合物1通过X射线晶体学、核磁共振谱和~(57)Fe Mo穆斯堡尔谱进行了表征,其特征是三苯甲基配体的η 5结合模式。配合物1是一个有效的Fe(0)合成子。例如,1与过量的CO反应导致形成[Fe(CO)5]和Gomberg二聚体。此外,1与5当量的P(OMe)3的反应导致形成Fe(0)配合物[(μ,η4:η4-Ph 2CC 6 H5 C6 H5 CPh 2){Fe(P(OMe)3)3}2](2),其特征在于通过η 4相互作用由两个[Fe 0(P(OMe)3)3]片段结合的Gomberg二聚体的新邻位异构体。
Treatment of Fe(OAc)2in THF with 2 equiv of Li(CPh3) at −25 °C results in the formation of [Fe(η5-CPh3)2] (1) in 22% yield. Complex1was characterized by X-ray crystallography, NMR spectroscopy, and57Fe Mössbauer spectroscopy and features an η5binding mode of its trityl ligands. Complex1functions as an effective Fe(0) synthon. For example, the reaction of1with excess CO results in the formation of [Fe(CO)5] and Gomberg’s dimer. Additionally, thermolysis of1with 5 equiv of P(OMe)3results in formation of the Fe(0) complex [(μ,η4:η4-Ph2CC6H5C6H5CPh2){Fe(P(OMe)3)3}2] (2), which features the novelo,o-isomer of Gomberg’s dimer bound by two [Fe0(P(OMe)3)3] fragments via η4interactions.