%0 Journal Article %1 Moscherosch.1995 %A Moscherosch, Michael %A Waldhoer, Eberhard %A Binder, Herbert %A Kaim, Wolfgang %A Fiedler, Jan. %D 1995 %J Inorganic Chemistry %K TCNB TCNE TCNQ ammine electrochem ligand;oxidn ligand;redn ligand;ruthenium redox ruthenium tetracyano tetranuclear %N 17 %P 4326--4335 %R 10.1021/ic00121a010 %T Tetranuclear Pentaammineruthenium Complexes Bridged by p-Conjugated Tetracyano Ligands Related to TCNE: Syntheses and Spectroscopy of Different Oxidation States %V 34 %X (μ4-TCNX)[Ru(NH3)5]4n+, TCNX = TCNE (tetracyanoethene), TCNQ (tetracyano-p-quinodimethane), TCNP (2,3,5,6-tetracyanopyrazine), and TCNB (1,2,4,5-tetracyanobenzene), were synthesized in the resp. (8+) states with PF6- (TCNE, TCNQ, TCNP) or CF3SO3- counterions (TCNB). IR, UV/visible/near-IR, and XPS spectroscopies were used to characterize the tetranuclear (8+) ions which exhibit four equiv. nitrile and pentaamminemetal groups and intense long-wavelength optical absorptions. The (8+) ions are easily oxidized to (10+) species and reduced stepwise to (7+) and (6+) ions; EPR, UV/visible/near-IR, and, in part, IR spectroelectrochem. techniques were applied to these oxidn. states in the case of the TCNE, TCNQ, and TCNB systems. The complexes may be described as fully delocalized sym. tetrametalla p systems (TCNXδ-)[RuII+δ/4(NH3)5]4n+ with partially reduced ligands and fractionally oxidized metal centers. The extent of metal-to-ligand electron transfer in the ground state is higher for the TCNQ and TCNE complexes than for the tetranuclear TCNP and TCNB compds. [on SciFinder(R)]

@article{Moscherosch.1995, abstract = {{(μ4-TCNX)[Ru(NH3)5]4}n+, TCNX = TCNE (tetracyanoethene), TCNQ (tetracyano-p-quinodimethane), TCNP (2,3,5,6-tetracyanopyrazine), and TCNB (1,2,4,5-tetracyanobenzene), were synthesized in the resp. (8+) states with PF6- (TCNE, TCNQ, TCNP) or CF3SO3- counterions (TCNB). IR, UV/visible/near-IR, and XPS spectroscopies were used to characterize the tetranuclear (8+) ions which exhibit four equiv. nitrile and pentaamminemetal groups and intense long-wavelength optical absorptions. The (8+) ions are easily oxidized to (10+) species and reduced stepwise to (7+) and (6+) ions; EPR, UV/visible/near-IR, and, in part, IR spectroelectrochem. techniques were applied to these oxidn. states in the case of the TCNE, TCNQ, and TCNB systems. The complexes may be described as fully delocalized sym. tetrametalla \textgreek{p} systems {(TCNXδ-)[RuII+δ/4(NH3)5]4}n+ with partially reduced ligands and fractionally oxidized metal centers. The extent of metal-to-ligand electron transfer in the ground state is higher for the TCNQ and TCNE complexes than for the tetranuclear TCNP and TCNB compds. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Moscherosch, Michael and Waldhoer, Eberhard and Binder, Herbert and Kaim, Wolfgang and Fiedler, Jan.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2ff745d1bd2d376870c66767f886c7e4c/huebleriac}, doi = {10.1021/ic00121a010}, interhash = {8f7b6095d99dce9bb93610fc115fde23}, intrahash = {ff745d1bd2d376870c66767f886c7e4c}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {TCNB TCNE TCNQ ammine electrochem ligand;oxidn ligand;redn ligand;ruthenium redox ruthenium tetracyano tetranuclear}, number = 17, pages = {4326--4335}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Tetranuclear Pentaammineruthenium Complexes Bridged by \textgreek{p}-Conjugated Tetracyano Ligands Related to TCNE: Syntheses and Spectroscopy of Different Oxidation States}, volume = 34, year = 1995 }