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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/3495
Title: Ruthenium(III) cyclometalates obtained by site-specific orthometallation and their reactivity with nitric oxide: Photoinduced release and estimation of no liberated from the ruthenium nitrosyl complexes
Authors: Ghosh, Kaushik
Kumar S.
Kumar R.
Singh U.P.
Published in: European Journal of Inorganic Chemistry
Abstract: Cyclometalated Ru III complexes [Ru(L SB1)(PPh 3) 2Cl] (1), [L SB1H 2 = 2-(3-nitrobenzylideneamino)phenol], and [Ru(L SB2)(PPh 3) 2Cl] (2), [L SB2H 2 = 4-methyl-2-(3-nitrobenzylideneamino)phenol and H = dissociable protons], were synthesized by site-specific orthometallation and characterized by spectroscopic and electrochemical studies. Complexes 1 and 2 were treated with in situ generated nitric oxide (NO), derived from an acidified nitrite solution, which afforded the ruthenium nitrosyl complexes [Ru(L SB3H)(PPh 3) 2(NO)Cl](ClO 4) (1a) and [Ru(L BOX)(PPh 3) 2(NO)Cl](ClO 4) (2a), respectively, [L SB3H 2 = 4-nitro-2-(3- nitrobenzylideneamino)phenol, L BOXH = 5-methyl-7-nitro-2-(3- nitrophenyl)benzoxazole and H = dissociable protons]. Complexes 1a and 2a were found to be diamagnetic and were characterized by 1H NMR and 31P NMR spectral studies. Both 1a and 2a exhibited V NO in the range 1800-1835 cm -1 in the IR spectra. Molecular structures of ω-aryl ruthenium nitrosyl complexes 1a·CH 3OH· 2CH 2Cl 2·H 2O and 2a·2CH 2Cl 2 were determined by X-ray crystallography. Nitrosylation at the metal centre, oxidative cyclization and ligand nitration were authenticated from the crystal structures. The redox properties of the metal centre were investigated. In both the nitrosyl complexes 1a and 2a, coordinated NO was found to be photolabile. The amount of photoreleased NO was estimated by using the Griess reagent and the data was compared with that obtained from sodium nitroprusside (SNP). The role of the nitro group in the ligand frame was discussed with regard to orthometallation, NO reactivity and photolability. Ruthenium(III) cyclometalates were synthesized by site-specific orthometallation. The reactivity of nitric oxide was investigated and the photolability of nitric oxide in newly synthesized ruthenium nitrosyl complexes was examined. The amount of photoreleased NO was estimated by using a Griess reagent in UV as well as in visible light. The role of the nitro group in the ligand frame was scrutinized. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Citation: European Journal of Inorganic Chemistry (2012), (6): 929-938
URI: https://doi.org/10.1002/ejic.201101026
http://repository.iitr.ac.in/handle/123456789/3495
Issue Date: 2012
Keywords: Metalation
Photolability
Redox chemistry
Ruthenium
ISSN: 14341948
Author Scopus IDs: 57204513823
7405769266
57208685185
57203181883
Author Affiliations: Ghosh, K., Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, Uttarakhand, India
Kumar, S., Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, Uttarakhand, India
Kumar, R., Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, Uttarakhand, India
Singh, U.P., Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, Uttarakhand, India
Corresponding Author: Ghosh, K.; Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667, Uttarakhand, India; email: ghoshfcy@iitr.ernet.in
Appears in Collections:Journal Publications [CY]

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