%0 Journal Article %1 Patra.2003 %A Patra, Srikanta %A Sarkar, Biprajit %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2003 %J Inorganic Chemistry %K 3 acetylacetonate complex complex;iminosemiquinone crystal electrochem electrochem;ruthenium iminoquinone iminothioquinone prepn redox;pentanedionate redox;valence ruthenium structure %N 20 %P 6469--6473 %R 10.1021/ic034469h %T Separating Innocence and Non-Innocence of Ligands and Metals in Complexes (L)Ru(acac)2n (n = -1, 0, +1; L = o-Iminoquinone or o-Iminothioquinone) %V 42 %X The diamagnetic complexes (L)Ru(acac)2 (L = o-iminoquinone or o-iminothioquinone) were obtained from Ru(acac)2(CH3CN)2 and 2-aminophenol or 2-aminothiophenol, resp. X-ray structure anal. of (L1)Ru(acac)2 (L1 = o-iminoquinone) revealed C-C intra-ring, C-O, and C-N distances which suggest a RuIII-iminosemiquinone oxidn. state distribution with antiparallel spin-spin coupling. One-electron oxidn. and redn. of both title compds. to paramagnetic monocations (L)Ru(acac)2+ or monoanions (L)Ru(acac)2- occurs reversibly at widely sepd. potentials (DE \textgreater 1.3 V) and leads to low-energy shifted charge transfer bands. In comparison with clearly established RuII-semiquinone or RuIII-catecholate systems the g tensor components 2.23 \textgreater g1 \textgreater 2.09, 2.16 \textgreater g2 \textgreater 2.07, and 1.97 \textgreater g3 \textgreater 1.88 point to considerable metal contributions to the singly occupied MO, corresponding to RuIII complexes with either o-quinonoid ($\rightarrow$ cations) or catecholate-type ligands ($\rightarrow$ anions) and only minor inclusion of RuIV- or RuII-iminosemiquinone formulations, resp. The preference for the RuIII oxidn. state for all accessible species is partially attributed to the monoanionic 2,4-pentanedionate (acac) co-ligands which favor a higher metal oxidn. state than, e.g., neutral 2,2'-bipyridine (bpy). on SciFinder(R)

@article{Patra.2003, abstract = {The diamagnetic complexes [(L)Ru(acac)2] (L = o-iminoquinone or o-iminothioquinone) were obtained from Ru(acac)2(CH3CN)2 and 2-aminophenol or 2-aminothiophenol, resp. X-ray structure anal. of (L1)Ru(acac)2 (L1 = o-iminoquinone) revealed C-C intra-ring, C-O, and C-N distances which suggest a RuIII-iminosemiquinone oxidn. state distribution with antiparallel spin-spin coupling. One-electron oxidn. and redn. of both title compds. to paramagnetic monocations [(L)Ru(acac)2]+ or monoanions [(L)Ru(acac)2]- occurs reversibly at widely sepd. potentials (\textgreek{D}E {\textgreater} 1.3 V) and leads to low-energy shifted charge transfer bands. In comparison with clearly established RuII-semiquinone or RuIII-catecholate systems the g tensor components 2.23 {\textgreater} g1 {\textgreater} 2.09, 2.16 {\textgreater} g2 {\textgreater} 2.07, and 1.97 {\textgreater} g3 {\textgreater} 1.88 point to considerable metal contributions to the singly occupied MO, corresponding to RuIII complexes with either o-quinonoid ($\rightarrow$ cations) or catecholate-type ligands ($\rightarrow$ anions) and only minor inclusion of RuIV- or RuII-iminosemiquinone formulations, resp. The preference for the RuIII oxidn. state for all accessible species is partially attributed to the monoanionic 2,4-pentanedionate (acac) co-ligands which favor a higher metal oxidn. state than, e.g., neutral 2,2'-bipyridine (bpy). [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Patra, Srikanta and Sarkar, Biprajit and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2a1a441b3f64e619b2db3b0d0817002d5/huebleriac}, doi = {10.1021/ic034469h}, interhash = {a7cc0a07316058d754f01d3fb306ac93}, intrahash = {a1a441b3f64e619b2db3b0d0817002d5}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {3 acetylacetonate complex complex;iminosemiquinone crystal electrochem electrochem;ruthenium iminoquinone iminothioquinone prepn redox;pentanedionate redox;valence ruthenium structure}, number = 20, pages = {6469--6473}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Separating Innocence and Non-Innocence of Ligands and Metals in Complexes [(L)Ru(acac)2]n (n = -1, 0, +1; L = o-Iminoquinone or o-Iminothioquinone)}, volume = 42, year = 2003 }