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Issue 35, 2009
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Main-chain organometallic polymers comprising redox-active iron(ii) centers connected by ditopic N-heterocyclic carbenes

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Abstract

Main-chain organometallic polymers were synthesized from bimetallic iron(II) complexes containing a ditopic N-heterocyclic carbene (NHC) ligand [(cp)(CO)LFe(NHC∼NHC)Fe(cp)(CO)L]X2 (where NHC∼NHC represents a bridging dicarbene ligand, L = I or CO). Addition of a diimine ligand such as pyrazine or 4,4′-bipyridine, interconnected these bimetallic complexes and gave the corresponding co-polymers containing iron centers that are alternately linked by a dicarbene and a diimine ligand. Diimine coordination depended on the wingtip groups at the carbene ligands and was accomplished either by photolytic activation of a carbonyl ligand from the cationic [Fe(cp)(NHC)(CO)2]+ precursor (alkyl wingtips) or by AgBF4-mediated halide abstraction from the neutral complex [FeI(cp)(NHC)(CO)] (mesityl wingtips). Remarkably, the polymeric materials were substantially more stable than the related bimetallic model complexes. Electrochemical analyses indicated metal–metal interactions in the pyrazine-containing polymers, whereas in 4,4′-bipyridine-linked systems the metal centers were electronically decoupled.

Graphical abstract: Main-chain organometallic polymers comprising redox-active iron(ii) centers connected by ditopic N-heterocyclic carbenes

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Supplementary files

Article information


Submitted
07 Apr 2009
Accepted
12 Jun 2009
First published
23 Jul 2009

Dalton Trans., 2009, 7168-7178
Article type
Paper

Main-chain organometallic polymers comprising redox-active iron(II) centers connected by ditopic N-heterocyclic carbenes

L. Mercs, A. Neels, H. Stoeckli-Evans and M. Albrecht, Dalton Trans., 2009, 7168
DOI: 10.1039/B907018D

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