Versatile Reactivity of Cyclic 1,2-Dimethylhydrazinodiphosphines

Abstract

A versatile reactivity from the cage compound P(NMeNMe) 3 P is presented. The Staudinger reaction with Me 3 SiN 3 is carried out. The crystal structure of the compound issued from the reaction on both sides (Me 3 SiN=P(NMeNMe) 3 P=NSiMe 3 ) is reported. When the reaction occurs on only one side, the remaining free phosphorus atom is complexed with RuCl 2 (p-cymene). P(NMeNMe) 3 P reacts with PCl 3 , leading to the heterocyclic compound ClP(NMeNMe) 2 PCl. This heterocycle also displays a versatile reactivity. Substitution reaction with HNiPr 2 leads to * Dr. J. P. Majoral

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

“…The 4-fold oxidation of 1Me and 1Et with Me 3 SiN 3 proved challenging, requiring between 3 and 4 months of heating the respective cage in excess azide at temperatures exceeding 100 °C. , While the reaction is inconvenient and potentially hazardous, the spectroscopic yield of the target tetra-silylphosphinimine cages, 3Me and 3Et , is quantitative, and they can be readily isolated by crystallization as pure substances directly from the reaction mixtures. The analogous oxidation of 2Me had been reported previously by Caminade to take 7 weeks (< 1 gram scale), but following optimization of this synthesis by us, the target bis-silylphosphinimine, 4Me , could be accessed on multigram scales within 48 h …”

“…83,92 While the reaction is inconvenient and potentially hazardous, the spectroscopic yield of the target tetrasilylphosphinimine cages, 3Me and 3Et, is quantitative, and they can be readily isolated by crystallization as pure substances directly from the reaction mixtures. The analogous oxidation of 2Me had been reported previously by Caminade to take 7 weeks (< 1 gram scale), 93 but following optimization of this synthesis by us, the target bis-silylphosphinimine, 4Me, could be accessed on multigram scales within 48 h. 94 Oxidized derivatives of 3R and 4Me are air-stable and can be handled in benchtop solvents. A battery of thermal, redox, and chemical stability tests also proved them to be exceptionally robust monomers.…”

A Robust, Divalent, Phosphaza-bicyclo[2.2.2]octane Connector Provides Access to Cage-Dense Inorganic Polymers and Networks

“…To access a more nucleophilic center, we considered capping the phosphorus vertices with silylimines containing a polar Si−N bond. Oxidation of 1 with [Me 3 Si][N 3 ] to give 3 had been reported by Caminade, 36 but the milligram-scale preparation required a 5-week reaction time, a Kugelrohr distillation, and ultimately gave only a 46% yield, motivating a synthetic redevelopment. We have optimized an improved procedure that yields 3 in >80% yield from 1 within 48 h on multi-gram scales (see SI), rendering it a practical starting material for further reactivity.…”

Rigid PN cages as 3-dimensional building blocks for crystalline or amorphous networked materials

“…The substituents at their nitrogen atoms can be tuned readily, offering an axis of structural control that is not easily available in hydrocarbon frameworks that feature strong C-C or C-H bonds. [11][12][13][14][15][16][17][18] Previous work has shown that compounds 1 and 2 can be oxidized at their P(III) vertices [19][20][21] with Me 3 SiN 3 (Staudinger reaction) to form new linear (3) or tetrahedral (4) connectors that can be copolymerized with element halides via Me 3 SiCl condensation. 22,23 However, not only is the synthesis of 3 and 4 hazardous (heating excess Me 3 SiN 3 above its boiling point) and lengthy (16 week reaction for 4), the obtained macromolecules also lack crystallinity and porosity, limiting their potential scope of applications.…”