Phenylimino quaternization of birdcage phosphorus compounds

Simple preparations of new monomeric trihalogenophosphine imides

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The oxidation of halogeno(2,4,6-tri-tert-butylphenylimino)phosphines [(2,4,C,H,) NPX, X = CI, Br or I] with dihalogens (CI,, Br, or I,) resulted in the formation of trihalogeno(N-2,4,6-tri-tert-butylpheny1)phosphine imides. The imides (2,4,6-But,C,H,) NPCI, and (2,4,6-Bu',C6H,) NPBr, were obtained quantitatively from the corresponding halogenoiminophosphine with PhlCI, and Br,, respectively, and were crystallographically characterized [(2,4,6-Bu',C,H,) N PCI,: Cm, a = 1 1.960(3), b = 14.696(2), c = 5.954(2) A, p = 97.71 (2)", Z = 2, R = 0.036, R' = 0.047; (2,4,6-But,C,H,)NPBr,: P2,lc.

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(PNSiMe3)4(NMe)6: A robust tetravalent phosphaza-adamantane scaffold for molecular and macromolecular chemistry

“…[23][24][25][26] Their quantitative, one-step, multi-gram synthesis from commodity reagents (PCl3, RNH2) is appealing from a practical perspective, and their high molecular symmetry makes them inherently suited for evolving a four-directional functional platform. Quadruple oxidation of some derivatives of C with azides, sulfur, and oxygen has also been reported, [27][28][29][30][31][32] but no subsequent reactivity was possible since the resulting compounds do not feature sufficiently labile bonds. Salts of the binary polyanion P4N6 10-have also been reported, but their high temperature solid-state synthesis (>600 o C elemental melt) and insolubility have precluded further use in synthetic chemistry.…”

(PNSiMe3)4(NMe)6: A robust tetravalent phosphaza-adamantane scaffold for molecular and macromolecular chemistry

“…[23][24][25][26] Their quantitative, one-step, multi-gram synthesis from commodity reagents (PCl3, RNH2) is appealing from a practical perspective, and their high molecular symmetry makes them inherently suited for evolving a four-directional functional platform. Quadruple oxidation of some derivatives of C with azides, sulfur, and oxygen has also been reported, [27][28][29][30][31][32] but no subsequent reactivity was possible since the resulting compounds do not feature sufficiently labile bonds. Salts of the binary polyanion P4N6 10have also been reported, but their high temperature solid-state synthesis (>600 o C elemental melt) and insolubility have precluded further use in synthetic chemistry.…”

“…The dramatic deceleration as a function of extent of oxidation is likely an electronic rather than steric effect, as it is also observed when the reaction is performed with a less hindered benzyl azide. 30 Even using a 10-fold excess of Me3SiN3, the reaction proved to be lethargic, requiring 12 weeks at 100 o C to achieve quantitative conversion to the tetraphosphinimine 2. Following removal of excess Me3SiN3 and recrystallization, 2 was reproducibly isolated in 60-80% crystalline yield and comprehensively characterized.…”