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Issue 45, 2010
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Tricarbonylrhenium(I) complexes of highly symmetric hexaazatrinaphthylene ligands (HATN): structural, electrochemical and spectroscopic properties

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Abstract

The new mononuclear and dinuclear tricarbonylrhenium(I) complexes [(HATN)Re(CO)3Cl] (1-Cl) and [(μ-Me6-HATN)[Re(CO)3Cl]2] (2-Cl2) of highly symmetric ligands HATN and Me6-HATN were synthesized and structurally characterized. X-Ray crystal structures reveal identical strained aromatic systems and out of the plane fac-Re(CO)3Cl units for both complexes. The packing geometry in the unit cell of 1 suggests intermolecular π–π association. Infrared spectroelectrochemistry (SEC) experiments confirmed ligand-based reductions. To get more insight into the reduction mechanism the triflate salts, [(HATN)Re(CO)3](OTf) (1-OTf) and [(μ-Me6HATN){Re(CO)3}2](OTf)2 (2-OTf2), were synthesized. Their electrochemical and spectroelectrochemical behavior also exhibits reduction of the aromatic systems. The electronic absorption spectral features of the one electron reduced species were studied by UV-vis-NIR spectroscopy, which shows a broad shoulder at 1500 nm, confirming intra-ligand charge transfer (ILCT). Density functional theory (DFT) calculations on the complexes 1-Cl and 2-Cl2 for structural optimization show good agreement with experimental bond lengths and bond angles. The spin density plot shows a metal based HOMO and HATN ligand centered LUMO.

Graphical abstract: Tricarbonylrhenium(i) complexes of highly symmetric hexaazatrinaphthylene ligands (HATN): structural, electrochemical and spectroscopic properties

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Publication details

The article was received on 03 Jul 2010, accepted on 31 Aug 2010 and first published on 18 Oct 2010


Article type: Paper
DOI: 10.1039/C0DT00780C
Citation: Dalton Trans., 2010,39, 10937-10943
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    Tricarbonylrhenium(I) complexes of highly symmetric hexaazatrinaphthylene ligands (HATN): structural, electrochemical and spectroscopic properties

    S. Roy and C. P. Kubiak, Dalton Trans., 2010, 39, 10937
    DOI: 10.1039/C0DT00780C

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