Title

Reversible C-C Bond Formation between Redox-Active Pyridine Ligands in Iron Complexes

Author Faculty (Discipline)

Science

Document Type

Article

Publication Date

12-19-2012

Early Online Version

11-26-2012

Journal

Journal of the American Chemical Society

Volume Number

134

Issue Number

50

Page Numbers

20352-20364

ISSN

0002-7863

Embargo Period

6-20-2013

Reportable Items (HERDC/ERA)

C1

Peer Review

Before publication

Abstract

This manuscript describes the formally iron(I) complexes LMeFe(Py-R)2 (LMe = bulky β-diketiminate; R = H, 4-tBu), in which the basal pyridine ligands preferentially accept significant unpaired spin density. Structural, spectroscopic, and computational studies on the complex with 4-tert-butylpyridine (tBupy) indicate that the S = 3/2 species is a resonance hybrid between descriptions as (a) high-spin iron(II) with antiferromagnetic coupling to a pyridine anion radical and (b) high-spin iron(I). When the pyridine lacks the protection of the tert-butyl group, it rapidly and reversibly undergoes radical coupling reactions that form new C–C bonds. In one reaction, the coordinated pyridine couples to triphenylmethyl radical, and in another, it dimerizes to give a pyridine-derived dianion that bridges two iron(II) ions. The rapid, reversible C–C bond formation in the dimer stores electrons from the formally reduced metal as a C–C bond in the ligands, as demonstrated by using the coupled diiron(II) complex to generate products that are known to come from iron(I) precursors. [from publisher's website].

Link to publisher version (DOI)

https://doi.org/10.1021/ja305679m

Comments

Due to copyright restrictions this article is unavailable for download.

Copyright © 2012 American Chemical Society

At the time of writing Gemma Christian was affiliated with the Max Planck Institute for Chemical Energy Conversion

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