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
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- 作者：Samaresh Bhattacharya ; Parna Gupta ; Falguni Basuli ; and Cortlandt G. Pierpont
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：November 4, 2002
- 年：2002
- 卷：41
- 期：22
- 页码：5810 - 5816
- 全文大小：106K
- 年卷期：v.41,no.22(November 4, 2002)
- ISSN：1520-510X
文摘
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 aspecific mode of coordination. This correlation between ligand charge and structure has been extended toiminoquinone and iminothioquinone ligands, giving a charge-localized view of electronic structure for complexes ofredox-active metal ions. The radical semiquinonate form of these ligands has been found to be a surprisinglycommon mode of coordination; however, the paramagnetic character of the radical ligand is often obscured incomplexes containing paramagnetic metal ions. In this report, diamagnetic iminosemiquinonate (isq) andiminothiosemiquinonate (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 forRu(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. Crystallographiccharacterization of Ru(PPh3)2(isq)Cl2, Ru(PPh3)2(itsq)Cl2, and Os(PPh3)2(ap)H2 was used to assign charge distributions.