Edge Article
Chemical Science
to D.J.D.). Michael J. Drummond was supported in the summer
2013 REU program at TAMU (CHE-1062840). The authors
acknowledge Dr Nattamai Bhuvanesh of the X-ray Diffraction
laboratory and Ryan D. Bethel at Texas A&M University for
helpful discussions.
Conclusions
For visualizing relationships between structure and reactivity,
Hammett correlations are a hallmark of physical organic and
physical organometallic chemistry. Such correlations in a
series of para substituted [(sIMes)(S–C6H4X)Fe(NO)2] DNICs
(compounds 1a–1e) with variations in the donor characteristics
of the aryl thiolate were used to provide a rmer experimental
foundation for the unusual theoretical proposal that an
oxidized {Fe(NO)2} moiety, i.e. {Fe(NO)2}9, served as a nucleo-
phile towards CO in a process that releases RSSR.40 Signicant
electronic rearrangement leads to a reduced {Fe(NO)2} product
in the form of [Fe(CO)(NO)2(NHC)].
Notes and references
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Acknowledgements
We are thankful for nancial support from the National Science
Foundation (CHE-1266097 to M.Y.D., CHE-1057743 to D.J.D.),
and the Robert A. Welch Foundation (A-0924 to M.Y.D., A-0923
This journal is © The Royal Society of Chemistry 2014
Chem. Sci., 2014, 5, 3795–3802 | 3801