Issue 35, 2009
From the journal:

Dalton Transactions

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

Laszlo Mercs,a   Antonia Neels,b   Helen Stoeckli-Evansc  and  Martin Albrecht*ad  

* Corresponding authors

a Department of Chemistry, University of Fribourg, Chemin du Musee 9, CH-1700 Fribourg, Switzerland
E-mail: martin.albrecht@unifr.ch
Fax: +41 263009738
Tel: +41 263008786

b XRD Application Lab, CSEM, Rue Jaquet Droz 1, CH-2000 Neuchâtel, Switzerland

c Institute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2009 Neuchâtel, Switzerland

d School of Chemistry and Chemical Biology, University College Dublin Belfield, Dublin 4, Ireland

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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Article information

DOI
https://doi.org/10.1039/B907018D
Article type
Paper
Submitted
07 Apr 2009
Accepted
12 Jun 2009
First published
23 Jul 2009

Dalton Trans., 2009, 7168-7178

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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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