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Issue 2, 2010
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Three-coordinate late transition metal fluorinated alkoxide complexes

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Abstract

Homoleptic fluorinated alkoxide complexes have been prepared from KOC4F9, 1, via salt metathesis routes. One four-coordinate K{K(18C6)}[Co(OC4F9)4], 2, and four three-coordinate complexes: {K(18C6)}[Fe(OC4F9)3], 3, {K(18C6)}[Co(OC4F9)3], 4, {K(18C6)}[Cu(OC4F9)3], 5, and {K(18C6)}[Zn(OC4F9)3], 6, have been prepared and all except 5 have been characterized crystallographically. Compounds 3, 4, and 6 are very rare examples of monomeric, trigonal alkoxide complexes. All compounds have been characterized with UV-vis and IR spectroscopy, solution magnetic susceptibility, and elemental analysis. In solution, compound 2 exists in an equilibrium with 4 and 1, which has been probed with cyclic voltammetry, supporting energetically different Co2+/Co3+ potentials in the three-coordinate (Ep,a = ∼1.2 V vs Fc/Fc+) and four-coordinate (Ep,a = ∼0.9 V) geometries. The ligand field engendered by the perfluoro-t-butoxide ligand has been studied with DFT calculations on 4 and the hypothetical [Co(OC4H9)3] as well as the previously reported [Co(mes)3] and [Co{N(TMS)2}3] showing significant π-type interactions in the xy plane as well as above and below for the two alkoxide species.

Graphical abstract: Three-coordinate late transition metal fluorinated alkoxide complexes

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Publication details

The article was received on 01 Jul 2009, accepted on 17 Sep 2009 and first published on 16 Oct 2009


Article type: Paper
DOI: 10.1039/B911758J
Citation: Dalton Trans., 2010,39, 374-383
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    Three-coordinate late transition metal fluorinated alkoxide complexes

    S. A. Cantalupo, J. S. Lum, M. C. Buzzeo, C. Moore, A. G. DiPasquale, A. L. Rheingold and L. H. Doerrer, Dalton Trans., 2010, 39, 374
    DOI: 10.1039/B911758J

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