%0 Journal Article %1 Das.2012g %A Das, Dipanwita %A Scherer, Thomas Michael %A Das, Amit %A Mondal, Tapan Kumar %A Mobin, Shaikh M. %A Fiedler, Jan %A Priego, Jose Luis %A Jimenez-Aparicio, Reyes %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2012 %J Dalton Transactions %K DFT bipyridine complex crystal electrochem electron iminobenzoquinone one osmium oxidn prepn;paramagnetic redn redox;spectroelectrochem state structure %N 38 %P 11675--11683 %R 10.1039/c2dt30903c %T The intricate paramagnetic state of Os(Q)2(bpy)+, Q = 4,6-di-tert-butyl-o-iminobenzoquinone %V 41 %X The combination of two highly noninnocent ligands with a 3rd-row transition metal produces the title complex ion which was crystd. as Os(Q)2(bpy)(ClO4)·C6H6 (Q = 4,6-di-tert-butyl-o-iminobenzoquinone, bpy = 2,2'-bipyridine) and could be structurally characterized to exhibit a tris-chelate situation at the metal with trans positioned N and cis positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q.bul.-)OsIII(Q.bul.-) can rationalize the obsd. S = 1/2 situation with ligand-centered resulting spin. Ligand-based spin is confirmed by DFT (calcd. spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g1 1.981, g2 1.955, g3 1.803, Dg 0.178, 〈g〉 1.915) which is influenced by the high spin-orbit coupling const. of the Os center. The susceptibility measurements reveal antiferromagnetic behavior. A 1-electron oxidn. and two 1-electron redns. could be monitored spectroelectrochem. (UV-visible-NIR) and analyzed by TD-DFT, in comparison with the results from the Ru analog. The anal. reflects the strong orbital mixing between the metal and the two Q-ligand MOs. on SciFinder(R)

@article{Das.2012g, abstract = {The combination of two highly noninnocent ligands with a 3rd-row transition metal produces the title complex ion which was crystd. as [Os(Q)2(bpy)](ClO4)·C6H6 (Q = 4,6-di-tert-butyl-o-iminobenzoquinone, bpy = 2,2'-bipyridine) and could be structurally characterized to exhibit a tris-chelate situation at the metal with trans positioned N and cis positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q.bul.-)OsIII(Q.bul.-) can rationalize the obsd. S = 1/2 situation with ligand-centered resulting spin. Ligand-based spin is confirmed by DFT (calcd. spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g1 1.981, g2 1.955, g3 1.803, \textgreek{D}g 0.178, 〈g〉 1.915) which is influenced by the high spin-orbit coupling const. of the Os center. The susceptibility measurements reveal antiferromagnetic behavior. A 1-electron oxidn. and two 1-electron redns. could be monitored spectroelectrochem. (UV-visible-NIR) and analyzed by TD-DFT, in comparison with the results from the Ru analog. The anal. reflects the strong orbital mixing between the metal and the two Q-ligand MOs. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Das, Dipanwita and Scherer, Thomas Michael and Das, Amit and Mondal, Tapan Kumar and Mobin, Shaikh M. and Fiedler, Jan and Priego, Jose Luis and Jimenez-Aparicio, Reyes and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f76a12cb2c5493fd61d84ae2557d2ac2/huebleriac}, doi = {10.1039/c2dt30903c}, interhash = {ab658bd7a6a945178cda107a61eb64c9}, intrahash = {f76a12cb2c5493fd61d84ae2557d2ac2}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {DFT bipyridine complex crystal electrochem electron iminobenzoquinone one osmium oxidn prepn;paramagnetic redn redox;spectroelectrochem state structure}, number = 38, pages = {11675--11683}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {The intricate paramagnetic state of [Os(Q)2(bpy)]+, Q = 4,6-di-tert-butyl-o-iminobenzoquinone}, volume = 41, year = 2012 }