%0 Journal Article %1 Choudhuri.2015 %A Choudhuri, Mohommad M. R. %A Behzad, Mahdi %A Al-Noaimi, Mousa %A Yap, Glenn P. A. %A Kaim, Wolfgang %A Sarkar, Biprajit %A Crutchley, Robert J. %D 2015 %J Inorganic Chemistry %K azobis complex complex;prepn complex;spectroelectrochem crystal dinuclear phenylcyanamido ruthenium salt;cyclic structure voltammetry %N 4 %P 1508--1517 %R 10.1021/ic502487x %T Variable Noninnocence of Substituted Azobis(phenylcyanamido)diruthenium Complexes %V 54 %X The synthetic chem. of substituted 4,4'-azobis(phenylcyanamide) ligands was investigated, and the complexes [Ru(tpy)(bpy)2(m-L)][PF6]2, where L = 2,2':5,5'-tetramethyl-4,4'-azobis(phenylcyanamido) (Me4adpc2-), 2,2'-dimethyl-4,4'-azobis(phenylcyanamido) (Me2adpc2-), unsubstituted (adpc2-), 3,3'-dichloro-4,4'-azobis(phenylcyanamido) (Cl2adpc2-), and 2,2':5,5'-tetrachloro-4,4'-azobis(phenylcyanamido) (Cl4adpc2-), were prepd. and characterized by cyclic voltammetry and visible-near-IR (NIR) and IR spectroelectrochem. The room temp. ESR spectrum of [Ru(tpy)(bpy)2(m-Me4adpc)]3+ showed an org. radical signal and is consistent with an oxidn.-state description [RuII, Me4adpc.bul.-, RuII]3+, while that of [Ru(tpy)(bpy)2(m-Cl2adpc)]3+ at 10 K showed a low-symmetry RuIII signal, which is consistent with the description [RuIII, Cl2adpc2-, RuII]3+. IR spectroelectrochem. data suggest that [Ru(tpy)(bpy)2(m-adpc)]3+ is delocalized and [Ru(tpy)(bpy)2(m-Cl2adpc)]3+ and [Ru(tpy)(bpy)2(m-Cl4adpc)]3+ are valence-trapped mixed-valence systems. A NIR absorption band that is unique to all [Ru(tpy)(bpy)2(m-L)]3+ complexes is obsd.; however, its energy and intensity vary depending on the nature of the bridging ligand and, hence, the complexes' oxidn.-state description. [on SciFinder(R)]

@article{Choudhuri.2015, abstract = {The synthetic chem. of substituted 4,4'-azobis(phenylcyanamide) ligands was investigated, and the complexes [{Ru(tpy)(bpy)}2(\textgreek{m}-L)][PF6]2, where L = 2,2':5,5'-tetramethyl-4,4'-azobis(phenylcyanamido) (Me4adpc2-), 2,2'-dimethyl-4,4'-azobis(phenylcyanamido) (Me2adpc2-), unsubstituted (adpc2-), 3,3'-dichloro-4,4'-azobis(phenylcyanamido) (Cl2adpc2-), and 2,2':5,5'-tetrachloro-4,4'-azobis(phenylcyanamido) (Cl4adpc2-), were prepd. and characterized by cyclic voltammetry and visible-near-IR (NIR) and IR spectroelectrochem. The room temp. ESR spectrum of [{Ru(tpy)(bpy)}2(\textgreek{m}-Me4adpc)]3+ showed an org. radical signal and is consistent with an oxidn.-state description [RuII, Me4adpc.bul.-, RuII]3+, while that of [{Ru(tpy)(bpy)}2(\textgreek{m}-Cl2adpc)]3+ at 10 K showed a low-symmetry RuIII signal, which is consistent with the description [RuIII, Cl2adpc2-, RuII]3+. IR spectroelectrochem. data suggest that [{Ru(tpy)(bpy)}2(\textgreek{m}-adpc)]3+ is delocalized and [{Ru(tpy)(bpy)}2(\textgreek{m}-Cl2adpc)]3+ and [{Ru(tpy)(bpy)}2(\textgreek{m}-Cl4adpc)]3+ are valence-trapped mixed-valence systems. A NIR absorption band that is unique to all [{Ru(tpy)(bpy)}2(\textgreek{m}-L)]3+ complexes is obsd.; however, its energy and intensity vary depending on the nature of the bridging ligand and, hence, the complexes' oxidn.-state description. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Choudhuri, Mohommad M. R. and Behzad, Mahdi and Al-Noaimi, Mousa and Yap, Glenn P. A. and Kaim, Wolfgang and Sarkar, Biprajit and Crutchley, Robert J.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2f86a3bcd55ece1a7d658baf7d2fd92b2/b_schwederski}, doi = {10.1021/ic502487x}, interhash = {c98ecff09df75b33dfe7ea7814bdb2e9}, intrahash = {f86a3bcd55ece1a7d658baf7d2fd92b2}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {azobis complex complex;prepn complex;spectroelectrochem crystal dinuclear phenylcyanamido ruthenium salt;cyclic structure voltammetry}, number = 4, pages = {1508--1517}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {Variable Noninnocence of Substituted Azobis(phenylcyanamido)diruthenium Complexes}, volume = 54, year = 2015 }