Bhattacharya, Samaresh ; Gupta, Parna ; Basuli, Falguni ; Pierpont, Cortlandt G. (2002) Structural systematics for o-C6H4XY ligands with X,Y= O, NH, and S donor atoms. o-iminoquinone and o-iminothioquinone complexes of ruthenium and osmium Inorganic Chemistry, 41 (22). pp. 5810-5816. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic025766%2B
Related URL: http://dx.doi.org/10.1021/ic025766+
Abstract
The structural features of quinone ligands are diagnostic of charge. The o-benzoquinone, radical semiquinonate, and catecholate electronic forms have C-O bond lengths and a pattern of ring C-C bond lengths that point to a specific mode of coordination. This correlation between ligand charge and structure has been extended to iminoquinone and iminothioquinone ligands, giving a charge-localized view of electronic structure for complexes of redox-active metal ions. The radical semiquinonate form of these ligands has been found to be a surprisingly common mode of coordination; however, the paramagnetic character of the radical ligand is often obscured in complexes containing paramagnetic metal ions. In this report, diamagnetic iminosemiquinonate (isq) and iminothiosemiquinonate (itsq) complexes of ls-d5 Ru(III) with related complexes of osmium are reported. With osmium, the Os(IV)-amidophenolate (ap) redox isomer is formed. Electrochemical and spectral properties are described for Ru(PPh3)2(isq)Cl2, Ru(PPh3)2(itsq)Cl2,Os(PPh3)2(ap)Br2, Os(PPh3)2(atp)Br2, and Os(PPh3)2(ap)H2. Crystallographic characterization of Ru(PPh3)2(isq)Cl2, Ru(PPh3)2(itsq)Cl2, and Os(PPh3)2(ap)H2 was used to assign charge distributions.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 1950 |
| Deposited On: | 08 Oct 2010 11:16 |
| Last Modified: | 21 Jan 2011 11:00 |
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