%0 Journal Article %1 GrossLannert.1989 %A Gross-Lannert, Renate %A Kaim, Wolfgang %A Lechner, Ulrike %A Roth, Eberhard %A Volger, Conny. %D 1989 %J Zeitschrift fuer Anorganische und Allgemeine Chemie %K arom elec electrochem orbital;redox oxidn phosphane phosphane;electron phosphorus potential reaction redn transfer %P 47--56 %T On the reaction of aromatic phosphanes with electrons. IV. Significance of low-lying orbitals at phosphorus for the mobility and coordinative characteristics of PR2 substituents in reduced p-phenylenediphosphanes %V 579 %X Dinuclear complexes of the ligands 1,4-R2P-C6H4-PR2 (R = Me, Ph) with the carbonylmetal fragments (C5H4CH3)Mn(CO)2 and M(CO)5 (M = Cr, Mo, W) were studied by cyclic voltammetry. The dimanganese complex shows reversible oxidn. to ESR-detectable MnII but no detectable splitting of the cyclic voltammetric wave, the p-phenylenediphosphane bridge does apparently not permit effective metal-metal interaction. The free ligands are reversibly reduced to persistent, ESR-detectable anion radicals with hindered rotation of the PR2 substituents. The carbonylmetal complexes, on the other hand, show dissocn. on electron uptake despite their less neg. redn. potentials. This behavior stands in contrast to main-group element complexes of these ligands and is attributed to the competition between the metal carbonyl fragment and the added electron for the low-lying unoccupied orbitals (s* at P. on SciFinder(R)

@article{GrossLannert.1989, abstract = {Dinuclear complexes of the ligands 1,4-R2P-C6H4-PR2 (R = Me, Ph) with the carbonylmetal fragments (C5H4CH3)Mn(CO)2 and M(CO)5 (M = Cr, Mo, W) were studied by cyclic voltammetry. The dimanganese complex shows reversible oxidn. to ESR-detectable MnII but no detectable splitting of the cyclic voltammetric wave, the p-phenylenediphosphane bridge does apparently not permit effective metal-metal interaction. The free ligands are reversibly reduced to persistent, ESR-detectable anion radicals with hindered rotation of the PR2 substituents. The carbonylmetal complexes, on the other hand, show dissocn. on electron uptake despite their less neg. redn. potentials. This behavior stands in contrast to main-group element complexes of these ligands and is attributed to the competition between the metal carbonyl fragment and the added electron for the low-lying unoccupied orbitals (\textgreek{s}* at P. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Gross-Lannert, Renate and Kaim, Wolfgang and Lechner, Ulrike and Roth, Eberhard and Volger, Conny.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2bc897626d7bb9b32ec9906cfc70e209c/huebleriac}, interhash = {5eae7af5c89b929c1b1711a700c12b57}, intrahash = {bc897626d7bb9b32ec9906cfc70e209c}, issn = {0044-2313}, journal = {Zeitschrift fuer Anorganische und Allgemeine Chemie}, keywords = {arom elec electrochem orbital;redox oxidn phosphane phosphane;electron phosphorus potential reaction redn transfer}, pages = {47--56}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {On the reaction of aromatic phosphanes with electrons. IV. Significance of low-lying orbitals at phosphorus for the mobility and coordinative characteristics of PR2 substituents in reduced p-phenylenediphosphanes}, volume = 579, year = 1989 }