Synthesis, characterization, and alkyne trimerization catalysis of a heteroleptic two-coordinate fe(i) complex

The synthesis of the first heteroleptic, two-coordinate Fe(I) complex IPr-Fe-N(SiMe3)DIPP (1) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; DIPP = 2,6-(i)Pr2-C6H3) is reported. Protonation of the Fe(II) bis(amido) complex Fe[N(SiMe3)DIPP]2 followed by addition of IPr and reduction by pota...

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Published inJournal of the American Chemical Society Vol. 137; no. 19; pp. 6366 - 6372
Main Authors Lipschutz, Michael I, Chantarojsiri, Teera, Dong, Yuyang, Tilley, T Don
Format Journal Article
LanguageEnglish
Published United States 20.05.2015
Subjects
Alkynes - chemistry
Catalysis
Cyclization
Imidazoles - chemical synthesis
Imidazoles - chemistry
Iron Compounds - chemical synthesis
Iron Compounds - chemistry
Models, Molecular
Spectroscopy, Mossbauer
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Summary:The synthesis of the first heteroleptic, two-coordinate Fe(I) complex IPr-Fe-N(SiMe3)DIPP (1) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; DIPP = 2,6-(i)Pr2-C6H3) is reported. Protonation of the Fe(II) bis(amido) complex Fe[N(SiMe3)DIPP]2 followed by addition of IPr and reduction by potassium graphite in a one-pot reaction results in good yields of 1. The redox activity of 1 and comparison between 1 and its reduction product by (57)Fe Mössbauer spectroscopy are discussed, and the reduction was found to be metal-based rather than ligand-based. The activity of 1 toward the catalytic cyclotrimerization of terminal and internal alkynes is described.
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ISSN:1520-5126
DOI:10.1021/jacs.5b02504