29104-67-4Relevant academic research and scientific papers
Nitric oxide reactivity of copper(ii) complexes of bidentate amine ligands: Effect of substitution on ligand nitrosation
Sarma, Moushumi,Mondal, Biplab
experimental part, p. 2927 - 2934 (2012/04/10)
Three copper(ii) complexes with bidentate ligands L1, L 2 and L3 [L1, N,N/- dimethylethylenediamine; L2, N,N/-diethylethylenediamine and L3, N,N/-diisobutylethylenediamine], respectively, were synthesized as their perchlorate salts. The single crystal structures for all the complexes were determined. The nitric oxide reactivity of the complexes was studied in acetonitrile solvent. The formation of thermally unstable [CuII-NO] intermediate on reaction of the complexes with nitric oxide in acetonitrile solution was observed prior to the reduction of copper(ii) centres to copper(i). The reduction was found to result with a simultaneous mono- and di-nitrosation at the secondary amine sites of the ligand. All the nitrosation products were isolated and characterized. The ratio of the yield of mono- and di-nitrosation product was found to be dependent on the N-substitution present in the ligand framework.
Reactivity of Nucleophilic Nitrogen Compounds towards the Nitroso Group
Garcia-Rio, Luis,Iglesias, Emilia,Leis, J. Ramon,Pena, M. Elena,Rios, Ana
, p. 29 - 37 (2007/10/02)
We discuss the reactivity of 43 nucleophilic nitrogen compounds towards the nitroso group of N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS), and in some cases with alkyl nitrites.The series of nucleophiles considered is structurally very varied, includes members exhibiting the alpha effect, and covers 8 pKa units and a range of reactivities of almost five orders of magnitude.The values of solvent isotope effects and activation parameters have been measured and throw light on the structure of the transition states involved.Reactivities do not correlate well with thebasicity of the nucleophile, largely owing to the behaviour of primary amines, ammonia and nucleophiles with an alpha effect.Application of the curve crossing model suggests a relationship with vertical ionization potentials.The relationship with Ritchie's N+ scale is discussed, and interesting correlations with the reactivities of the same nucleophiles in various other chemical processes are noted.
