%0 Journal Article %1 Khusniyarov.2008 %A Khusniyarov, Marat M. %A Harms, Klaus %A Burghaus, Olaf %A Sundermeyer, Joerg %A Sarkar, Biprajit %A Kaim, Wolfgang %A van Slageren, Joris %A Duboc, Carole %A Fiedler, Jan. %D 2008 %J Dalton Transactions %K antiferromagnetic complex complex;crystal complex;cyclic complex;fluorophenylphenylenediamine complexation deriv exchange fluorophenylphenylenediamido metal metal;transition oxidn prepn structure transition voltammetry %N 10 %P 1355--1365 %R 10.1039/b714974c %T A series of metal complexes with the non-innocent N,N'-bis(pentafluorophenyl)-o-phenylenediamido ligand: Twisted geometry for tuning the electronic structure %X 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)

@article{Khusniyarov.2008, abstract = {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)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Khusniyarov, Marat M. and Harms, Klaus and Burghaus, Olaf and Sundermeyer, Joerg and Sarkar, Biprajit and Kaim, Wolfgang and {van Slageren}, Joris and Duboc, Carole and Fiedler, Jan.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/25b9ae7274f6c4ceffaa86ef98e570a31/huebleriac}, doi = {10.1039/b714974c}, interhash = {d8525cb51fa1385dff942bd957f5d1d9}, intrahash = {5b9ae7274f6c4ceffaa86ef98e570a31}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {antiferromagnetic complex complex;crystal complex;cyclic complex;fluorophenylphenylenediamine complexation deriv exchange fluorophenylphenylenediamido metal metal;transition oxidn prepn structure transition voltammetry}, number = 10, pages = {1355--1365}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {A series of metal complexes with the non-innocent N,N'-bis(pentafluorophenyl)-o-phenylenediamido ligand: Twisted geometry for tuning the electronic structure}, year = 2008 }