Abstract
Dimeric cyclophosphazanes [{P(μ-NR)}2(μ-NR)]2 [R = (t)Bu ( 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-N(t)Bu)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-N(i)Pr)5(μ-NH)Se4 ( 4), showed only one substituent loss. Theoretical studies confirmed the steric nature of the driving force underlying the different outcomes.
Highlights
Cyclophosph(III/III)azanes, with a variety of substituents, have been extensively studied over the past decades.[1]
Balakrishna et al reported the synthesis of a series of cyclophosph(V/V)azanes showing enhanced air and moisture stability.[10]
We report the unexpected C–N bond activation that occurs upon oxidation of the dimeric cyclophosphazanes [{P(m-NtBu)}2(m-NtBu)]2 (1) with elemental Se
Summary
Cyclophosph(III/III)azanes, with a variety of substituents, have been extensively studied over the past decades.[1]. We report the unexpected C–N bond activation that occurs upon oxidation of the dimeric cyclophosphazanes [{P(m-NtBu)}2(m-NtBu)]2 (1) with elemental Se. Compound 1, was previously synthesized via the condensation reaction between [ClP(m-NtBu)]2 and [LiNtBuP(m-NtBu)]2, and was isolated as co-crystals of [LiNtBuP(m-NtBu)]2 1 (1 : 1 ratio) by Chivers et al.[11] Our initial work focused on the purification of 1, which was successfully crystalized in THF at room temperature.
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