Elsevier

Inorganica Chimica Acta

Volume 312, Issues 1–2, 29 January 2001, Pages 231-238
Inorganica Chimica Acta

Note
Synthesis, characterisation and co-polymerisation of ruthenium 1,2-naphthoquinone-1-oxime complexes containing 4-vinylpyridine ligands

https://doi.org/10.1016/S0020-1693(00)00337-6Get rights and content

Abstract

Ruthenium 1,2-naphthoquinone-1-oxime (1-nqoH) complexes cis,cis-[Ru{η2-N(O)C10H6O}2(CO)(vpy)] (3) and trans,cis-[Ru{η2-N(O)C10H6O}2(CO)(vpy)] (4) were synthesised by substituted decarbonylation reactions of dicarbonyl complexes cis,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (1) and trans,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (2), respectively. In addition, a dipyridine product trans,trans-[Ru{η2-N(O)C10H6O}2(vpy)2] (5) was also obtained in both reaction routes as the result of a ligand rearrangement during the substitution process of the second carbonyl ligand. The molecular structure of 3 was established by X-ray analysis. Co-polymerisation reactions were conducted on 3 with styrene as the co-monomer. The metal-containing moieties maintain the coordination geometry of the starting monomer 3 on the carbon-backbone chain.

Introduction

Coordination chemistry of 1,2-naphthoquinone-mono-oxime (nqoH) with transition metals has attracted much attention [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11]. However, most of the studies are concerned with first-row transition metals. Recently, we have demonstrated the coordination reaction of nqoH with second-row transition metals, including ruthenium [1], [2], [3], [4] and rhodium [5]. The complexes obtained display rich reactivity, as well as electrochemical properties. The reaction between triruthenium dodecacarbonyl and 1,2-naphthoquinone-1-oxime (1-nqoH) led to the formation of isostructural mononuclear complexes cis,cis- (cis-NO, cis-O) (1) and trans,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (trans-NO, cis-O) (2) [1]. The carbonyl groups in the complexes are readily replaced by some nitrogen or phosphorus donor ligands and thus functional groups with designed features could be introduced into the metal coordination sphere, providing the complexes with various properties [1], [2], [3], [4].

Polymers incorporating transition metal complexes have been of interest to chemists. These metal-containing polymers have good potential in a variety of technological applications, such as heterogeneous catalysis [12], [13] and a wide range of molecular devices [14], [15], [16], [17]. Four methods have been adopted for the inclusion of metal complexes into polymer structures: (1) binding via a coordination bond from a polymer-bound ligand [14]; (2) covalent attachment by reaction of a functionalised complex with a functionalised polymer [12], [13]; (3) homopolymerisation of metal-containing monomers incorporating polymerisable groups [13], [18], [19], [20]; and (4) co-polymerisation of a complex bearing a polymerisable group with selected co-monomers [12], [13], [17], [19], [20], [21], [22]. Recently, we have demonstrated an immobilised osmium cluster through co-polymerisation with styrene [21].

In this paper, we report the synthesis and characterisation of some ruthenium complexes containing a vinylpyridine group and 1-nqoH ligands. Immobilisation of the metal complex has also been obtained through co-polymerisation with styrene.

Section snippets

Synthesis

The addition of 1 equiv. of trimethylamine N-oxide into the 1:1 mixture of cis,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (1) or trans,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (2) and 4-vinylpyridine (vpy) in CH2Cl2 at room temperature leads to an instantaneous colour change from orange to brown. A reddish-brown product cis,cis-[Ru{η2-N(O)C10H6O}2(CO)(vpy)] (3) or trans,cis-[Ru{η2-N(O)C10H6O}2(CO)(vpy)] (4) was isolated through thin-layer chromatography (TLC) separation in which one of the carbonyl groups in the

Experimental

All synthetic manipulations were carried out under nitrogen with standard Schlenk techniques. Chemicals were purchased from commercial sources and used as received unless stated otherwise. The parent complexes of cis,cis- and trans,cis-[Ru{η2-N(O)C10H6O}2(CO)2] (1 and 2) were prepared according to our previously described procedure [1]. Trimethylamine N-oxide (Aldrich) was dried by azeotropic distillation and sublimed prior to use. Benzoyl peroxide was recrystallised from CHCl3 in methanol

Supplementary material

Supplementary data are available from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, on request, quoting the deposition number 144818 (fax: +44-1223-336033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).

Acknowledgements

We gratefully acknowledge financial support from the Hong Kong Research Grants Council and the University of Hong Kong. X.-X.L. acknowledges the receipt of a demonstratorship administered by the Department of Chemistry, the University of Hong Kong.

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