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

Roy, Amit Saha ; Muresan, Nicoleta ; Tuononen, Heikki M. ; Rath, Sankar P. ; Ghosh, Prasanta (2008) Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states Dalton Transactions (26). p. 3438. ISSN 1477-9226

Full text not available from this repository.

Official URL: http://doi.org/10.1039/B802063A

Related URL: http://dx.doi.org/10.1039/B802063A

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.

Item Type:Article
Source:Copyright of this article belongs to Royal Society of Chemistry.
ID Code:120928
Deposited On:07 Jul 2021 07:16
Last Modified:07 Jul 2021 07:16

Repository Staff Only: item control page