“…1,3,2-Diazaphospholes and 1,3,2-Diazaphospholides 1,3,2-Diazaphospholes with an isolated ring have been prepared from diaminomaleonitrile and PCl 3 [10,11] . Reacting both components in refluxing acetonitrile Treatment of 1 or 2 with secondary amines, or of diaminomaleonitrile with P(NMe 2 ) 3 , gave the bicyclic phosphatriazapentalene 4 [12] .…”
Section: Synthesis Via Heterocyclic Ring Assemblymentioning
This chapter gives a survey on five-and six-membered phosphorusnitrogen heterocyclic compounds whose rings combine a phosphazene (>N-P = N-) or phosphazane (>N-P(X)-N<) unit with an unsaturated C 2 or C 3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N -heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.
“…1,3,2-Diazaphospholes and 1,3,2-Diazaphospholides 1,3,2-Diazaphospholes with an isolated ring have been prepared from diaminomaleonitrile and PCl 3 [10,11] . Reacting both components in refluxing acetonitrile Treatment of 1 or 2 with secondary amines, or of diaminomaleonitrile with P(NMe 2 ) 3 , gave the bicyclic phosphatriazapentalene 4 [12] .…”
Section: Synthesis Via Heterocyclic Ring Assemblymentioning
This chapter gives a survey on five-and six-membered phosphorusnitrogen heterocyclic compounds whose rings combine a phosphazene (>N-P = N-) or phosphazane (>N-P(X)-N<) unit with an unsaturated C 2 or C 3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N -heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.
“…An early example is the ring closure reaction of dimethylammonium 4,5-dicyano-1,3,2-diazaphospholide 114 , prepared from the condensation of diaminomaleodinitrile with P(NMe 2 ) 3 , with secondary amines which affords 4,6-bis(dialkylamino)-1,3,5-triaza-2-phosphapentalenes 115 (Scheme ). A similar reaction takes place with 2-chloro-dihydro-diazaphosphole 116 . , 37 …”
Section: Synthesis By Anellation Of a Heterophosphole
Ringmentioning
confidence: 86%
“…Related olefins are not stable. Another route is to build up the anellated ring from reactions of functionally substituted heterophospholes, but due to the high reactivity of PC or PN bonds in many heterophospholes, attempts to use this strategy have been made only very rarely. − …”
Section: Synthetic Routesmentioning
confidence: 99%
“…This method has been only rarely used. First examples were pyrrolo-anellated 1,3,2-diazaphospholes formed by the reaction of dimethylammonium 4,5-dicyano-1,3,2-diazaphospholide with secondary amines. , Other interesting examples are the syntheses of phospha-analogous nucleobases with phosphorus replacing one of the N atoms of the five-membered ring by fusion reactions of functionally substituted 1,3-azaphospholes with formamidinium acetate, formamide, or urea affording 1,3-azaphospholo-pyrimidines…”
“…As such, chloromethyl dichlorophosphine ClCH 2 PCl 2 turned out to be useful, and also methylene bis(dichlorophosphine) CH 2 (PCl 2 ) 2 . Azaphospholes 36-39 were synthesized [106][107][108][109][110], including anellated ones for which the 2-phosphaindolizines 40 and their aza-analogs 41-43 stand as examples [94,[110][111][112][113][114].…”
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