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

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.