Cargando…

A Synthetic Model of Enzymatic [Fe(4)S(4)]–Alkyl Intermediates

[Image: see text] Although alkyl complexes of [Fe(4)S(4)] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this chal...

Descripción completa

Detalles Bibliográficos
Autores principales: Ye, Mengshan, Thompson, Niklas B., Brown, Alexandra C., Suess, Daniel L. M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6748666/
https://www.ncbi.nlm.nih.gov/pubmed/31373801
http://dx.doi.org/10.1021/jacs.9b06975
Descripción
Sumario:[Image: see text] Although alkyl complexes of [Fe(4)S(4)] clusters have been invoked as intermediates in a number of enzymatic reactions, obtaining a detailed understanding of their reactivity patterns and electronic structures has been difficult owing to their transient nature. To address this challenge, we herein report the synthesis and characterization of a 3:1 site-differentiated [Fe(4)S(4)](2+)–alkyl cluster. Whereas [Fe(4)S(4)](2+) clusters typically exhibit pairwise delocalized electronic structures in which each Fe has a formal valence of 2.5+, Mössbauer spectroscopic and computational studies suggest that the highly electron-releasing alkyl group partially localizes the charge distribution within the cubane, an effect that has not been previously observed in tetrahedrally coordinated [Fe(4)S(4)] clusters.