Reactivity of a Stable Phosphinonitrene towards Small Molecules

Abstract

The room-temperature stable phosphinonitrene 1 undergoes a thermal rearrangement into heterocycle 2 through a process involving a nitrene insertion into a CH bond. In the presence of acetonitrile, a nitrene-acetonitrile adduct has been isolated; then it first rearranges into a ketenimine and subsequently into a rare example of diazaphosphete. Compound 1 also splits water, carbon dioxide, carbon disulfide, and elemental sulfur, although it reacts with white phosphorus, leading to a P5 N cluster formally resulting from the insertion of the PN moiety into a P-P edge of the P4 tetrahedron.

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

“…Therefore, OPN is more reactive than N 2 O, as indicated by its reversible coupling reaction with CO, as nitrenes and heavier phosphinidenes do. Given the very recently discovered reactions of nitrenes and phosphinidenes with other small molecules such as O 2 , H 2 , and H 2 O, their reactions with OPN, as a potent interstellar species, should be of great interest, which are currently under investigations.…”

Applications of N-heterocyclic imines in main group chemistry

“…The addition of an excess amount of acetonitrile to the phosphinonitrene (71) afforded a mixture (16 : 1) of the ketenimine 85 and the diazaphosphete 86 (Scheme 21). 39 Notably, the ketenimine is transformed into the diazaphosphete at elevated temperature (90 1C). This process was reasoned by the initial deprotonation of acetonitrile by the nitrenic centre and nucleophilic attack of the generated cyanomethylanion at the phosphorus atom to afford 85.…”

“…Reaction of the phosphinonitrene (71) with carbon dioxide or carbon disulfide yields the isocyanate 87 or the isothiocyanate 88, respectively (Scheme 21). 39 One should point out the cleavage of the thermodynamically stable CQE double bond (E = O, S) in this process. Compound 71 activates elemental sulfur (S 8 ), as well as white phosphorus (P 4 ).…”

Carbodiphosphorane mediated synthesis of a triflyloxyphosphonium dication and its reactivity towards nucleophiles

“…27 Cation 10 2+ is the first crystallographically characterized example of an isothiocyanatophosphonium cation and displays a distorted tetrahedral bonding environment at the P (NCS) atom. Its P(1)–N(1A) bond length (1.663(7) Å) is shorter than those of neutral tetra-coordinated isothiocyanate-substituted P V compounds ((ImN) 2 P(NCS)S (ImN = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-imine): 1.728(1) Å, 28 (ferrocene)P(NMe 2 )(NCS)S: 1.700(5) Å); 29 a slightly more acute P(1)–N(1A)–C(50A) angle (148.9(6)°) is observed ((ImN) 2 P(NCS)S: 162.0(1)°, (ferrocene)P(NMe) 2 (NCS)S: 156.5(6)°). Analogously to dications 1 2+ and 7 2+ –9 2+ , a shortened C(1)–P(1) bond is observed as the result of the electronic congestion of the substituents (Table 1).…”