Reactivities of cyclonickellated complexes with hydroxylamines: formation of κO-hydroxylamine and κN-imine adducts and a κO, κN-aminoxide derivative

Abstract

This report discusses the reactivities of hydroxylamines with a family of nickellacyclic complexes prepared by C–H nickellation of aryl phosphinites. Treating the dimeric complexes κ^C,κ^P-{2-OPR₂,4-R′-C₆H₄}₂Ni₂(μ-Br)₂ (R = i-Pr; R′ = H, Cl, OMe, NMe₂) or their monomeric acetonitrile adducts κ^C,κ^P-{2-OPR₂,4-R′-C₆H₄}Ni(Br)(NCMe) with hydroxylamines showed three types of reactivities depending on the Ni complex, the reaction solvent, and the substrate used: (1) the benzyl-protected substrate PhCH₂ONH₂ gave simple N-bound adducts with all Ni complexes; (2) the parent Ni dimer (R′ = H) reacted with Et₂NOH and (PhCH₂)₂NOH in CH₂Cl₂ to give, respectively, the zwitterionic amine oxide κ^C,κ^P-{2-OPR₂-C₆H₅}Ni(κ^O-ONHEt₂)Br and the bidentate aminoxide (i-R₂POPh)Ni{κ^O,κ^N-ON(CH₂Ph)₂}Br; (3) the analogous reaction of substituted Ni complexes (R′ = Cl, OMe, NMe₂) with hydroxylamines in acetonitrile gave adducts of imines derived from dehydration of Et₂NOH and (PhCH₂)₂NOH. The latter reactivity proceeds optimally in acetonitrile, but it also occurs to a lesser extent in C₆D₆ if the reaction is allowed to go for more than 24 h. Different mechanistic scenarios have been considered to rationalize the observed hydroxylamine → imine transformation.