A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions FeII, CoII, NiII, PdII, PtII, and AgI

Calvin E. Uzelmeier; Bradley W. Smucker; Eric W. Reinheimer; Mikhail Shatruk; Amanda W. O'Neal; Marc Fourmigué; Kim R. Dunbar

doi:10.1039/B610659E

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A series of complexes of the phosphorus-based TTF ligando-P2 with the metal ions Fe^II, Co^II, Ni^II, Pd^II, Pt^II, and Ag^I

Calvin E. Uzelmeier,^a Bradley W. Smucker,^a Eric W. Reinheimer,^a Mikhail Shatruk,^a Amanda W. O'Neal,^a Marc Fourmigué^ab and Kim R. Dunbar*^a

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* Corresponding authors

^a Department of Chemistry, Texas A & M University, College Station, TX, USA

^b Laborataire Chimie, Ingénierie Moléculaire et Materiaux (CIMMA), UMR 6200, CNRS, Université ď Angers, Bât K, UFR Sciences, 2 Bd Lavoisier, Angers, France

Abstract

Reactions of 3,4-dimethyl-3′,4′-bis(diphenylphosphino)tetrathiafulvalene, o-P2, with [BF₄]⁻ salts of Fe(II), Co(II), Ni(II), Pd(II), and Pt(II) yield complexes of general formula [M(o-P2)₂][BF₄]₂. Similar reactions between o-P2 and AgSbF₆ or AgPF₆ produced the salts [Ag(o-P2)₂][X] where X = [SbF₆]⁻ or [PF₆]⁻. The resulting compounds were fully characterized by ¹H and ³¹P{¹H} NMR, infrared and electronic absorption spectroscopies, cyclic voltammetry, FAB-MS and single-crystal X-ray diffraction. The paramagnetic Co(II) compound exhibits an S = 3/2 state with large spin–orbit coupling contribution at higher temperatures and an effective S′ = 1/2 state below 20 K. Electrochemical studies of the compounds indicate that the two functionalized TTF ligands are not in electronic communication and that they essentially behave as isolated redox centers.

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Supplementary files

Crystal structure data TXT (225K)

Article information

DOI: https://doi.org/10.1039/B610659E
Article type: Paper
Submitted: 25 Jul 2006
Accepted: 06 Sep 2006
First published: 19 Oct 2006

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Dalton Trans., 2006, 5259-5268

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A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions Fe^II, Co^II, Ni^II, Pd^II, Pt^II, and Ag^I

C. E. Uzelmeier, B. W. Smucker, E. W. Reinheimer, M. Shatruk, A. W. O'Neal, M. Fourmigué and K. R. Dunbar, Dalton Trans., 2006, 5259 DOI: 10.1039/B610659E

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Dalton Transactions