A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions FeII, CoII, NiII, PdII, PtII, and AgI
- 19 October 2006
- journal article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- No. 44,p. 5259-5268
- https://doi.org/10.1039/b610659e
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.Keywords
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