Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

Abstract

Chlorocyclophosphazene (Cl2P=N)3 und (Cl2p = N)4 reagieren mit Dihydraazidophosphorsäure‐derivaten in THF in Gegenwart von Triethylamin zu den Spiroverbindungen Cl4N3P3(NHN(CH3))2P(S)OC6H5, Ci6N4P4(NHNH)2P(s) OC6H5. Die Konstitutionen der neuen Verbindungen wurden durch IR‐, NMR‐ und Massenspektren sowie durch Elementaranalysen belegt.

Vinyl-type polymerization of norbornene by a nickel-based catalyst with phosphoraneiminato ligands

“…In dilute solutions there are indications for a stepwise dissociation of the heterocubanes down to monomers of type A and B, respectively. For a metal-nitrogen triple bond, bonding mode A implies such a (r, 2p) donor set of the NPR 3 ligand as it is also observed for the g 5 -bonded cyclopentadienyl ligand, so that both ligand types can be considered to be isolobal with one another: 19) . Replacement of catalysts of the cyclopentadienyl type by corresponding phosphoraneiminato complexes therefore seems to us to be an interesting and promising catalytic variant, particularly since these complexes are known in a great variety and are easily accessible under preparative aspects 18) .…”

Fluoride Ion Induced Reactions of Silicon−Oxygen and Silicon−Sulfur Bonds with Hexafluorocyclotriphosphazenes: Synthesis, Reactivity, and X-ray Structural Analyses of Sulfur/Oxygen-Containing Monospirofluorophosphazenes,

“…Halogen replacement reactions of N 3 P 3 Cl 6 are carried out primarily by reaction with (i) diol or diamine in the presence of a base that acts as a hydrochloride scavenger or (ii) with an alkali metal salt of the diol. These reactions are known to follow numerous pathways, and a variety of products can be isolated from a single reaction. − On the other hand, N 3 P 3 F 6 reacts with organo/organometallic lithium reagents in a much cleaner fashion vis - à - vis the chloro counterpart by minimizing the side reactions such as coordination of metal to skeletal nitrogen, P−N bond cleavage, and metal−halogen exchange. The advantage of using fluorophosphazenes can be ascribed to the fact that a more electronegative halogen bonded to the phosphorus atom decreases the Lewis basicity of the lone pair on the ring nitrogen atoms, thus preventing skeletal ring cleavage reactions.…”

“…The diversity of phosphazene chemistry can be attributed to the varied reactivity of the phosphorus−halogen bond toward different nucleophiles. For example, the reactions of N 3 P 3 Cl 6 with bifunctional reagents such as diols, diamines, amino alcohols, etc., can proceed along at least five different pathways. − Replacement of the halogen atoms by a dinucleophile may occur as follows: (a) in a geminal manner to give spirocyclic phosphazenes; (b) on two different phosphazene rings to form bridged phosphazenes; (c) by a monofunctional path, leaving one end of the dinucleophile unreacted thereby giving a pendent or dangling species; (d) in a nongeminal fashion on the same phosphazene ring to form a transannular (ansa) derivative; (e) by formation of polymeric phosphazenes (Scheme ). In addition to spirocycle formation, degradation of the N 3 P 3 ring also results when catechol is used as a bifunctional reagent. , When o -aminophenol is used, only degradation products are obtained. , The chemistry of bridged and dangling phosphazenes comprises the least studied class of phosphazene compounds and the data presented in the literature regarding the characterization of bridged phosphazenes are contradictory. , We have recently reported the isolation and first structural characterization of a polyfluoroalkoxy bridged phosphazene in which two N 3 P 3 units substituted by parafluorophenoxy groups are linked by an −OCH 2 CF 2 CF 2 CH 2 O− group .…”