Steric C-N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2

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Steric C-N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2

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Title: Steric C-N bond activation on the dimeric macrocycle [{P(μ-NR)}2(μ-NR)]2
Author: Shi, Yan X.; Liang, Rong Z.; Martin, Katherine A.; Star, Daniel G.; Díaz Álvarez, Jesús; Lin, Xin Y.; Ganguly, Rakesh; García García, Felipe
Abstract: Dimeric cyclophosphazanes [{P(μ-NR)}2(μ-NR)]2 [R = tBu ( 1) and iPr ( 3)] were oxidized with elemental selenium. During these reactions an unexpected C–N bond cleavage and N–H bond formation occurred. Compound 1 produced P4(μ-NtBu)3(μ-NH)3Se4 ( 2) where three tBu groups were lost in the form of isobutylene. In contrast, during the oxidation of the less sterically hindered 3, the resulting product, P4(μ-NiPr)5(μ-NH)Se4 ( 4), showed only one substituent loss. Theoretical studies confirmed the steric nature of the driving force underlying the different outcomes.
Date: 2015

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