title: Three-coordinate late transition metal fluorinated alkoxide complexes.
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 (E(p,a) = approximately 1.2 V vs Fc/Fc+) and four-coordinate (E(p,a) = approximately 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 -type interactions in the xy plane as well as above and below for the two alkoxide species.
authors.affiliation: Boston University, Chemistry Department, 590 Commonwealth Ave, Boston, MA 02215, USA.
authors.forename: Stefanie A
authors.initials: SA
authors.lastname: Cantalupo
authors.forename: June S
authors.initials: JS
authors.lastname: Lum
authors.forename: Marisa C
authors.initials: MC
authors.lastname: Buzzeo
authors.forename: Curtis
authors.initials: C
authors.lastname: Moore
authors.forename: Antonio G
authors.initials: AG
authors.lastname: DiPasquale
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Linda H
authors.initials: LH
authors.lastname: Doerrer