Homoleptic fluorinated alkoxide complexes have been prepared from KOC4F9, 1, viasalt 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 5have been characterized crystallographically. Compounds 3, 4, and 6are 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 2exists in an equilibrium with 4and 1, which has been probed with cyclic voltammetry, supporting energetically different Co2+/Co3+potentials in the three-coordinate (Ep,a= ∼1.2 V vsFc/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 4and 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 xyplane as well as above and below for the two alkoxide species. [ABSTRACT FROM AUTHOR]