Chemistry of some ruthenium phenolates: Synthesis, structure and redox properties
Resource
Polyhedron 19 (14): 1673-1680
Journal
Polyhedron
Journal Volume
19
Journal Issue
14
Pages
1673-1680
Date Issued
2000
Author(s)
Abstract
Reaction of three phenolate ligands, viz. 2,4,6-tribromophenol (HL1, where H stands for the phenolic proton), 2-nitrophenol (HL2) and 2,4,6-trinitrophenol (HL3O), with [Ru(PPh3)3Cl2] in a 2:1 molar ratio in the presence of a base gives complexes of type [Ru(PPh3)2(L)2] (L = L1, L2 and L3). The 2,4,6-tribromophenolate ligand (L1) binds to ruthenium as a bidentate O,Br-donor, while the 2-nitrophenolate ligand (L2) acts as a bidentate O,O-donor. 2,4,6-Trinitrophenol (HL3O) undergoes oxygen loss from one nitro group at the ortho position and coordinates to ruthenium in the 2-nitroso-4,6-dinitrophenolate (L3) form through the nitroso nitrogen and phenolate oxygen. The structures of the [Ru(PPh3)2(L1)2] and [Ru(PPh3)2(L3)2] complexes have been solved by X-ray crystallography. In [Ru(PPh3)2(L1)2] the coordination sphere around ruthenium is O2P2Br2 with a trans-cis-cis disposition of the three sets of donor atoms, respectively. In [Ru(PPh3)2(L3)2] ruthenium has a N2O2P2 coordination sphere with a cis-cis-trans arrangement of the three sets of donor atoms, respectively. The [Ru(PPh3)2(L)2] complexes are diamagnetic (low-spin d6, S = 0) and in acetonitrile solution show intense MLCT transitions in the visible region. Cyclic voltammetry on the [Ru(PPh3)2(L)2] complexes shows a reversible ruthenium(II)-ruthenium(III) oxidation within 0.63-0.71 V versus SCE followed by an irreversible ruthenium(III)-ruthenium(IV) oxidation near 1.5 V versus SCE. (C) 2000 Elsevier Science Ltd.
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journal article
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