Patra, Srikanta ; Sarkar, Biprajit ; Mobin, Shaikh M. ; Kaim, Wolfgang ; Lahiri, Goutam Kumar (2003) 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) Inorganic Chemistry, 42 (20). pp. 6469-6473. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic034469h
Related URL: http://dx.doi.org/10.1021/ic034469h
Abstract
The diamagnetic title complexes were obtained from Ru(acac)2(CH3CN)2 and 2-aminophenol or 2-aminothiophenol. X-ray structure analysis of (L1)Ru(acac)2 (L1 = ο -iminoquinone) revealed C-C intra-ring, C-O, and C-N distances which suggest a RuIII-iminosemiquinone oxidation state distribution with antiparallel spin-spin coupling. One-electron oxidation and reduction of both title compounds to paramagnetic monocations [(L)Ru(acac)2]+ or monoanions [(L)Ru(acac)2]- occurs reversibly at widely separated potentials (Δ E > 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 > g1 > 2.09, 2.16 > g2 > 2.07, and 1.97 > g3 > 1.88 point to considerable metal contributions to the singly occupied MO, corresponding to RuIII complexes with either o-quinonoid (→ cations) or catecholate-type ligands (→ anions) and only minor inclusion of RuIV- or RuII-iminosemiquinone formulations, respectively. The preference for the RuIII oxidation state for all accessible species is partially attributed to the monoanionic 2,4-pentanedionate (acac) co-ligands which favor a higher metal oxidation state than, e.g., neutral 2,2'-bipyridine (bpy).
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 88404 |
| Deposited On: | 28 Mar 2012 10:00 |
| Last Modified: | 28 Mar 2012 10:00 |
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