%0 Journal Article %1 Chatterjee.2009 %A Chatterjee, Sudipta %A Singh, Priti %A Fiedler, Jan %A Bakova, Radka %A Zalis, Stanislav %A Kaim, Wolfgang %A Goswami, Sreebrata. %D 2009 %J Dalton Transactions %K complex complex;ESR complex;electronic complex;electrooxidn complex;electroredn complex;geometry complex;osmium complex;valence crystal optimized osmium prepn prepn;UV quinonediimine ruthenium structure structure;ruthenium visible %N 37 %P 7778--7785 %R 10.1039/b906913e %T Effect of metal exchange (Os vs. Ru) and co-ligand variation (Cl- vs. acac-) on the oxidation state distribution in complexes of an o-phenylenediamido(2-)/o-quinonediimine redox system %X The compds. OsCl2L2 (1), RuCl2L2 (2) and Ru(acac)2L (3), L° = N-phenyl-o-quinonediimine and acac- = 2,4-pentanedionato, were synthesized and electrochem., spectroscopically and structurally characterized with the support of detailed DFT calcns. For the new Os compd. 1, the av. values for C:NH (1.331 \AA), C:NPh (1.345 \AA) and C:C (meta) bond lengths at 1.360 \AA agree more with an o-semiquinonediimine than with an o-quinonediimine formulation for the coordinated ligand, whereas the latter assignment is more appropriate to describe the Ru analog 2 (av. bond lengths of 1.308, 1.324, and 1.348 \AA, resp.). In turn, the corresponding av. bond lengths in 3 (1.333, 1.352, and 1.350 \AA, resp.) are suggestive of an o-semiquinonediimine ligand. DFT calcns. confirm the structural data and describe the electronic structures related to the oxidn. state assignments. The stabilization of trivalent Ru by electron donating acac- in 3 = RuIII(acac)2(L·-) and the preference of Os for higher oxidn. states (here: OsIVCl2(L·-)2 in 1) as compared to Ru analogs (here: RuIICl2(L°)2 in 2) in otherwise similar setting is responsible for these results. Oxidn. of the diamagnetic complexes proceeds to partly EPR and UV-visible spectroelectrochem. detectable cations with metal-centered spin, suggesting the following formulations: OsIIICl2(L°)2+ for 1+, RuIIICl2(L°)2+ for labile 2+, and RuIII(acac)2(L°)+ for 3+. In the case of 3, reversible metal-centered redn. results in ligand-based spin as compatible with a RuII(acac)2(L·-)- situation for 3-. on SciFinder(R)

@article{Chatterjee.2009, abstract = {The compds. OsCl2L2 (1), RuCl2L2 (2) and Ru(acac)2L (3), L° = N-phenyl-o-quinonediimine and acac- = 2,4-pentanedionato, were synthesized and electrochem., spectroscopically and structurally characterized with the support of detailed DFT calcns. For the new Os compd. 1, the av. values for C:NH (1.331 {\AA}), C:NPh (1.345 {\AA}) and C:C (meta) bond lengths at 1.360 {\AA} agree more with an o-semiquinonediimine than with an o-quinonediimine formulation for the coordinated ligand, whereas the latter assignment is more appropriate to describe the Ru analog 2 (av. bond lengths of 1.308, 1.324, and 1.348 {\AA}, resp.). In turn, the corresponding av. bond lengths in 3 (1.333, 1.352, and 1.350 {\AA}, resp.) are suggestive of an o-semiquinonediimine ligand. DFT calcns. confirm the structural data and describe the electronic structures related to the oxidn. state assignments. The stabilization of trivalent Ru by electron donating acac- in 3 = RuIII(acac)2(L·-) and the preference of Os for higher oxidn. states (here: OsIVCl2(L·-)2 in 1) as compared to Ru analogs (here: RuIICl2(L°)2 in 2) in otherwise similar setting is responsible for these results. Oxidn. of the diamagnetic complexes proceeds to partly EPR and UV-visible spectroelectrochem. detectable cations with metal-centered spin, suggesting the following formulations: [OsIIICl2(L°)2]+ for 1+, [RuIIICl2(L°)2]+ for labile 2+, and [RuIII(acac)2(L°)]+ for 3+. In the case of 3, reversible metal-centered redn. results in ligand-based spin as compatible with a [RuII(acac)2(L·-)]- situation for 3-. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Chatterjee, Sudipta and Singh, Priti and Fiedler, Jan and Bakova, Radka and Zalis, Stanislav and Kaim, Wolfgang and Goswami, Sreebrata.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f0fe383261dd5a8922e54d89c729c7ca/b_schwederski}, doi = {10.1039/b906913e}, interhash = {00c0575ac5e250732a4d83f47899e198}, intrahash = {f0fe383261dd5a8922e54d89c729c7ca}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {complex complex;ESR complex;electronic complex;electrooxidn complex;electroredn complex;geometry complex;osmium complex;valence crystal optimized osmium prepn prepn;UV quinonediimine ruthenium structure structure;ruthenium visible}, number = 37, pages = {7778--7785}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {Effect of metal exchange (Os vs. Ru) and co-ligand variation (Cl- vs. acac-) on the oxidation state distribution in complexes of an o-phenylenediamido(2-)/o-quinonediimine redox system}, year = 2009 }