Journal article
DFT Prediction and Experimental Investigation of Valence Tautomerism in Cobalt-Dioxolene Complexes
GK Gransbury, ME Boulon, S Petrie, RW Gable, RJ Mulder, L Sorace, R Stranger, C Boskovic
Inorganic Chemistry | AMER CHEMICAL SOC | Published : 2019
Abstract
The family of complexes of general formula [Co(Me n tpa)(Xdiox)] + (tpa = tris(2-pyridylmethyl)amine, n = 0-3 corresponds to successive methylation of the 6-position of the pyridine rings; X = Br 4 , Cl 4 , H 4 , 3,5-Me 2 , 3,5-tBu 2 ; diox = dioxolene) was investigated by density functional theory (DFT) calculations to predict the likelihood of valence tautomerism (VT). The OPBE functional with relativistic and solvent corrections allowed accurate reproduction of trends in spin-state energetics, affording the prediction of VT in complex [Co(Me 3 tpa)(Br 4 diox)] + (1 + ). One-electron oxidation of neutral precursor [Co II (Me 3 tpa)(Br 4 cat)] (1) enabled isolation of target compounds 1(PF ..
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Awarded by Australian Research Council
Funding Acknowledgements
We thank the Australian Research Council for financial support (DP150100353) to C.B. and L.S.; G.K.G. acknowledges the support of an Elizabeth and Vernon Puzey Scholarship from the Univ. of Melbourne and an Australian Government Research Training Award. L.S. and M.E.B. acknowledge the financial support from Italian MIUR through Project No. PRIN 2015-HYFSRT. Part of this research was undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.