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Tris-(1,3-diaryltriazenide) complexes of rhodium — Synthesis, structure and, spectral and electrochemical properties

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Abstract

Reaction of 1,3-diaryltriazenes (abbreviated in general as HL-R, where R stands for the para-substituent in the aryl fragment and H stands for the dissociable hydrogen atom, R = OCH3, CH3, H, Cl, NO2) with [Rh(PPh3)2(CO)Cl] in ethanol in the presence of NEt3 produces a series of tris-diaryltriazenide complexes of rhodium of type [Rh(L-R)3], where the triazenes are coordinated to rhodium as monoanionic, bidentate N,N-donors. Structure of the [Rh(L-OCH3)3] complex has been determined by X-ray crystallography. The complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. They also fluoresce in the visible region under ambient condition while excited at around 400 nm. Cyclic voltammetry on these complexes shows a Rh(III)-Rh(IV) oxidation (within 0·84–1·67 V vs SCE), followed by an oxidation of the coordinated triazene ligand (except the R = NO2 complex). An irreversible reduction of the coordinated triazene is also observed for all the complexes below −1·03 V vs SCE.

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Authors and Affiliations

  1. Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata, 700 032, USA

    Chhandasi Guharoy & Samaresh Bhattacharya

  2. Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK

    Michael G. B. Drew

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  1. Chhandasi Guharoy
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  2. Michael G. B. Drew
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  3. Samaresh Bhattacharya
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Correspondence to Samaresh Bhattacharya.

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Guharoy, C., Drew, M.G.B. & Bhattacharya, S. Tris-(1,3-diaryltriazenide) complexes of rhodium — Synthesis, structure and, spectral and electrochemical properties. J Chem Sci 121, 257–266 (2009). https://doi.org/10.1007/s12039-009-0028-5

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  • DOI: https://doi.org/10.1007/s12039-009-0028-5

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