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Light-activated generation of nitric oxide (NO) and sulfite anion radicals (SO 3 ˙ - ) from a ruthenium(ii) nitrosylsulphito complex.

Authors :
Roveda AC Jr
Santos WG
Souza ML
Adelson CN
Gonçalves FS
Castellano EE
Garino C
Franco DW
Cardoso DR
Source :
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2019 Aug 07; Vol. 48 (29), pp. 10812-10823. Date of Electronic Publication: 2019 Jul 08.
Publication Year :
2019

Abstract

This manuscript describes the preparation of a new Ru(ii) nitrosylsulphito complex, trans-[Ru(NH <subscript>3</subscript> ) <subscript>4</subscript> (isn)(N(O)SO <subscript>3</subscript> )] <superscript>+</superscript> (complex 1), its spectroscopic and structural characterization, photochemistry, and thermal reactivity. Complex 1 was obtained by the reaction of sulfite ions (SO <subscript>3</subscript> <superscript>2-</superscript> ) with the nitrosyl complex trans-[Ru(NH <subscript>3</subscript> ) <subscript>4</subscript> (isn)(NO)] <superscript>3+</superscript> (complex 2) in aqueous solution resulting in the formation of the N-bonded nitrosylsulphito (N(O)SO <subscript>3</subscript> ) ligand. To the best of our knowledge, only four nitrosylsulphito metal complexes have been described so far (J. Chem. Soc., Dalton Trans., 1983, 2465-2472), and there is no information about the photochemistry of such complexes. Complex 1 was characterized by spectroscopic means (UV-Vis, EPR, FT-IR, <superscript>1</superscript> H- and <superscript>15</superscript> N-NMR), elemental analysis and single-crystal X-ray diffraction. The X-ray structure of the precursor complex 2 is also discussed in the manuscript and is used as a reference for comparisons with the structure of 1. Complex 1 is water-soluble and kinetically stable at pH 7.4, with a first-order rate constant of 3.1 × 10 <superscript>-5</superscript> s <superscript>-1</superscript> for isn labilization at 298 K (t <subscript>1/2</subscript> ∼ 373 min). Under acidic conditions (1.0 M trifluoroacetic acid), 1 is stoichiometrically converted into the precursor complex 2. The reaction of hydroxide ions (OH <superscript>-</superscript> ) with 1 and with 2 yields the Ru(ii) nitro complex trans-[Ru(NH <subscript>3</subscript> ) <subscript>4</subscript> (isn)(NO <subscript>2</subscript> )] <superscript>+</superscript> with second-order rate constants of 2.1 and 10.5 M <superscript>-1</superscript> s <superscript>-1</superscript> (at 288 K), respectively, showing the nucleophilic attack of OH <superscript>-</superscript> at the nitrosyl in 2 (Ru-NO) and at the nitrosylsulphito in 1 (Ru-N(O)SO <subscript>3</subscript> ). The pK <subscript>a</subscript> value of the -SO <subscript>3</subscript> moiety of the N(O)SO <subscript>3</subscript> ligand in 1 was determined to be 5.08 ± 0.06 (at 298 K). The unprecedented photochemistry of a nitrosylsulphito complex is investigated in detail with 1. The proposed mechanism is based on experimental (UV-Vis, EPR, NMR and Transient Absorption Laser Flash Photolysis) and theoretical data (DFT) and involves photorelease of the N(O)SO <subscript>3</subscript> <superscript>-</superscript> ligand followed by formation of nitric oxide (NO˙) and sulfite radicals (SO <subscript>3</subscript> ˙ <superscript>-</superscript> , sulfur trioxide anion radical).

Details

Language :
English
ISSN :
1477-9234
Volume :
48
Issue :
29
Database :
MEDLINE
Journal :
Dalton transactions (Cambridge, England : 2003)
Publication Type :
Academic Journal
Accession number :
31282910
Full Text :
https://doi.org/10.1039/c9dt01432b