- Reactions of organozinc thiolates with nitrosonium ion: C -nitroso formation by possible transnitrosation
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The organometallic complexes [ZnPAThEt] and [ZnPAThMes], where PATh is 2-methyl-1-[methyl-(2-pyridin-2-yl-ethyl)amino]propane-2-thiolate, were prepared and their reactions with NOBF4 investigated. Formation of C-nitrosoethane and C-nitrosomesitylene, respectively, was established, and structural characterization of the latter by X-ray crystallography conclusively proved the dimeric nature of [MesNO]2 in the solid state. A transnitrosation pathway for C-nitroso formation is proposed based on theoretical calculations.
- Kozhukh, Julia,Fedoce Lopes, Juliana,Dos Santos, Helio F.,Lippard, Stephen J.
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p. 8063 - 8066
(2013/02/22)
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- Monomer-Dimer Solution Equilibria of 2,4,6-Trialkylnitrosobenzenes and 2,4,6-Trialkylnitrosobenzene/Nitrosobenzene Mixtures. A Study Using One- and Twodimensional NMR Techniques
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2,4,6-Trimethylnitrosobenzene in CDCl3 exists as a mixture of monomer and Z- and E-azodioxy dimers.The dissociation kinetics of both dimers were measured by one-dimensional time-dependent NMR spectroscopy on non-equilibrium solutions, and by two-dimensional exchange spectroscopy (2D-EXSY) on equilibrium solutions. 2,4,6-Tri-t-butylnitrosobenzene is entirely monomeric in CDCl3 but forms mixed azodioxy dimers in the presence of nitrosobenzene.The dissociation kinetics of the mixed E-dimer were followed by NMR techniques.The activation energy parameters for these dissociation equilibria were compared with previous data on related nitrosobenzene and dimethylnitrosobenzene systems.
- Orrell, Keith G.,Stephenson, David,Verlaque, James H.
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p. 1297 - 1303
(2007/10/02)
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