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Issue 26, 2008
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Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states

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Abstract

The synthesis, structure and spectroscopic properties of a complex salt [CoIII(gha)(PPh3)2][CoIICl3(PPh3)]·C2H5OH (1) are reported; gha = glyoxalbis(2-hydroxyanil). This is the first single crystal X-ray structure of a (gha)2 complex with a transition element. Though the determined bond parameters and UV-Vis spectroscopic data correlate well with a diradical description for the cation in 1, detailed electronic structure calculations using density functional theory confirm that [Co(gha)(PPh3)2]+ can be described as a closed shell singlet species which nevertheless displays an interesting electronic structure with significant electron transfer to the formally unoccupied LUMO of the square planar [Co(gha)]+ fragment. It was found that without the phosphine coligands, the [Co(gha)]+ unit has a triplet ground state with the lowest energy singlet diradical state lying only 1 kcal mol−1 higher in energy. The chemistry of the gha ligand is of interest as a spin diverse redox active system.

Graphical abstract: Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states

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Publication details

The article was received on 05 Feb 2008, accepted on 20 May 2008 and first published on 09 Jun 2008


Article type: Paper
DOI: 10.1039/B802063A
Citation: Dalton Trans., 2008,0, 3438-3446
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    Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states

    A. S. Roy, N. Muresan, H. M. Tuononen, S. P. Rath and P. Ghosh, Dalton Trans., 2008, 0, 3438
    DOI: 10.1039/B802063A

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