Issue 2, 2010
From the journal:

Dalton Transactions

Three-coordinate late transition metal fluorinated alkoxide complexes†

Stefanie A. Cantalupo,a   June S. Lum,a   Marisa C. Buzzeo,b   Curtis Moore,c   Antonio G. DiPasquale,d   Arnold L. Rheingoldc  and  Linda H. Doerrer*a  

* Corresponding authors

a Boston University, Chemistry Department, 590 Commonwealth Ave, Boston, MA, USA
E-mail: doerrer@bu.edu
Fax: +1 (0)617-353-6466
Tel: +1 (0)617-358-4335

b NSF Center for Electron Transport in Molecular Nanostructures, Columbia University, New York, NY, USA
E-mail: mb648@columbia.edu
Fax: +1 (0) 212-854-1909
Tel: +1 (0) 212-854-6163

c University of California, 9500 Gilman Drive, San Diego, CA, USA
E-mail: arnrhein@chem.ucsd.edu
Fax: +1 (0)858-3872
Tel: +1 (0)858-822-3870

d University of California, Berkeley, 32 Lewis Hall, Berkeley, CA, USA
E-mail: adipasqu@berkeley.edu
Fax: +1 (0)510-642-9675
Tel: +1 (0)510-642-8444

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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Article information

DOI
https://doi.org/10.1039/B911758J
Article type
Paper
Submitted
01 Jul 2009
Accepted
17 Sep 2009
First published
16 Oct 2009

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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