A series of metal complexes with the non-innocent N,N'-bis(pentafluorophenyl)-o-phenylenediamido ligand: twisted geometry for tuning the electronic structure.
A series of homoleptic complexes with non-innocent ligands derived from N,N'-bis(pentafluorophenyl)-o-phenylenediamine (H2Fpda) are reported. [NiII(Fsbqdi)2] (1), [PdII(Fsbqdi)2] (2), [CoII(Fsbqdi)2] (3), and [CuII(Fsbqdi)2] (4) were synthesized, where (Fsbqdi)1- represents a radical anion formed by one-electron oxidn. of the doubly deprotonated H2Fpda. The oxidn. states of ligands and metals in complexes 1-4 were assigned by single crystal X-ray crystallog. performed at low temps. Complex 4 is the first CuII complex where both o-phenylenediamine derived ligands are monoanionic radicals. The bulky N-C6F5 substituents force the complexes 1, 3, and 4 to adopt a twisted geometry (intermediate between square-planar and tetrahedral). The electronic structures of the neutral compds. 1-4 and of some of their cationic and/or anionic neighboring redox states were probed using EPR and UV-VIS-NIR spectroelectrochem. The twisted geometry of the complexes results in considerable changes in their electronic structures compared to the well known square-planar complexes while the strongly electron withdrawing N-C6F5 groups have a great influence on redox properties. [on SciFinder(R)]
Références
- Titre
- A series of metal complexes with the non-innocent N,N'-bis(pentafluorophenyl)-o-phenylenediamido ligand: twisted geometry for tuning the electronic structure.
- Type de publication
- Article de revue
- Année de publication
- 2008
- Auteurs
- Khusniyarov, Marat M., Harms Klaus, Burghaus Olaf, Sundermeyer Joerg, Sarkar Biprajit, Kaim Wolfgang, van Slageren Joris, Duboc Carole, and Fiedler Jan.
- Revue
- Dalt. Trans.
- Pagination
- 1355–1365
- ISSN
- 1477-9226
- Mots-clés
- antiferromagnetic exchange transition metal fluorophenylphenylenediamido complex crystal structure transition metal fluorophenylphenylenediamido complex cyclic voltammetry transition metal fluorophenylphenylenediamido complex fluorophenylphenylenediamine deriv prepn oxidn complexation transition metal transition metal fluorophenylphenylenediamido complex prepn structure
- DOI
- 10.1039/b714974c
Soumis le 12 avril 2018