2,4,6‐Tri(hydroxy)‐1,3,5‐triphosphinine, P3C3(OH)3: The Phosphorus Analogue of Cyanuric Acid

Suter, Riccardo; Mei, Yanbo; Baker, Matthew G.; Benkő, Zoltán; Li, Zhongshu; Grützmacher, Hansjörg

doi:10.1002/anie.201610156

Cited by 61 publications

(102 citation statements)

References 72 publications

(37 reference statements)

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“…This observation, and the fact that the sodium salts can be handled in water with limited hydrolysis (t 1/2 at 298 Kofa0.5 to 0.7 m solution ca. [6] Thenature of the carbonate can be varied and anumber of other carbonates are also synthetically viable,f or example,d imethyl or diethyl carbonate.T he dioxane content of the resulting product strongly depends on how long the solid is treated under vacuum, and can be determined by 31 Por 1 HNMR spectroscopy relative to an internal standard. [5] Thesynthesis of Na(dioxane) x (OCP) (where x = 1-5) was optimized by Grützmacher and co-workers in 2014, allowing for am ulti-gram synthesis of the salt from inexpensive precursors (sodium, red phosphorus, t BuOH, ethylenecarbonate) in high yields (typically > 80 %).…”

Section: Known Syntheses Of the Ocp à Ionmentioning

confidence: 99%

“…[28] In this particular case,t he chemistry of the 2-phosphaethynolate anion closely mimics that of its lighter congener the cyanate ion, as such transformations are reminiscent of Wçhlers historic synthesis of urea from the reaction of silver cyanate with ammonium chloride. [31] This latter species is prepared from the reaction of the commercially available (À)-B-chlorodiisopinocampheylborane,( ipc) 2 BCl, with Na-(dioxane) 2.5 (OCP), which is postulated to give aphosphaethynoaltoborane,(ipc) 2 B À O À C P, that spontaneously trimerizes. [30] Ap hosphorus-containing analogue of cyanuric acid, P 3 C 3 (OH) 3 ,w as reported in 2017 from the alcoholysis of the derivatized cyclic compound P 3 C 3 [OB(icp) 2 ] 3 (where ipc = diisopinocampheyl;S cheme 3d).…”

Section: Acid-base Chemistry and The Synthesis Of Ocphmentioning

confidence: 99%

“…[35] Coordination of the OCP À anion to am etal centre via the oxygen atom also permits for the reductive dimerization of two OCP À units to afford the formally tetra-anionic [OCPPCO] 4À ligand, which has recently been achieved from the reduction of the scandium complex {CH[N(Dipp)C(CH 3 )] 2 }Sc(ODipp)(THF)(OCP) (D;F igure 2). [31] Theh igh oxophilicity of boron favours formation of phosphaethynolate-type compounds;h owever even in the case of [(CH) 2 (NDipp) 2 C]B(OCP) (F), the phosphorus-bonded isomer is predicted to be thermodynamically more stable by computational methods.A sw ith phosphaethynolate compounds of the actinides and scandium, there is an enhanced reactivity of the formal P Ctriple bond, which allows for such species to be rationalized as phospha-alkyne analogues.F or example,the cyclic trimerization of (icp) 2 BÀOÀCPisclosely related to the trimerization of t Bu À C Ptoafford triphosphabenzene type species. [36] As with the known transition-metal compounds,coordination through the phosphorus atom with acute E À P À Cbond angles is observed in all cases.Bycontrast, there is only one known structurally authenticated example of aphosphaethynolate compound of amain-group element reported to date,[(CH) 2 (NDipp) 2 C]B-(OCP) (F;F igure 2).…”

Section: Coordination Chemistry and Salt Metathesismentioning

confidence: 99%

“…[66] Goicoechea and co-workers described the synthesis ar elated diphosphirene. Coordinating solvents such as THF cause adimerization of this compound (accompanied by boryl group migration to afford an eutral five-membered heterocycle featuring adirect P À Pbond (d 31 . In this case,t he reaction was found to be strongly solvent dependent.…”

Section: Three-membered Heterocyclesmentioning

confidence: 99%

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The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Known Syntheses Of the Ocp à Ionmentioning

confidence: 99%

Section: Acid-base Chemistry and The Synthesis Of Ocphmentioning

confidence: 99%

Section: Coordination Chemistry and Salt Metathesismentioning

confidence: 99%

Section: Three-membered Heterocyclesmentioning

confidence: 99%

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The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…Thet hreemembered 2p-electron delocalized heterocycle I [13] and the two four-membered heterocycles II [14a] and III [13] can be viewed as [2+ +1] or [2+ +2] cycloaddition products containing intact OCP units. [14b,c] Thesix-membered heterocycles are the products of [2+ +2+ +2] (IV, [15] V [16] )o r[ 2 + +4] cycloadditions (VI [15] ), respectively,w hich are likewise formed by incorporating ac omplete (OCP) À anion into the cycle. [14c] Thef ive-membered heterocycles VII-IX are special because they are formed in reactions between carboxylic acid chloride derivatives,RC(= X)Cl (X = NR, O, S) with two (OCP) À anions,but only one is fully included while the other serves as source of a" P À "i on after loss of CO. [17] Herein we report as imple access to annulated 1,3,4-azadiphospholes with aw idely tunable p-conjugated electronic structure, which have,i nc ontrast to well-studied diazaphospholes, [18] only rarely been investigated before.…”

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confidence: 99%

Annulated 1,3,4‐Azadiphospholides: Heterocycles with Widely Tunable Optical Properties

2017

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Phosphorus heterocycles find applications in the synthesis of p-conjugated compounds and as precursors for optoelectronic materials such as organic light-emitting diodes (OLEDs), electronic switches,a nd transistors.Ahigh-yield, one-pot synthesis of anionic annulated 1,3,4-azadiphospholides from Na(OCP) and 2-chloropyridines is presented. The synthesis proceeds without the use of transition metals and tolerates aw ide range of substrates.C yano-substituted compounds are especially deeply colored and have absorption maxima which range from l max = 525 to 596 nm. The optical properties are dominated by the spatial separation of an electron acceptor and donor unit within one molecule (pushpull chromophore). The anionic 1,3,4-azadiphospholides are silylated to neutral siloxy compounds with astrong blue-shifted absorption. This reaction can be reversed by addition of fluoride ions,w hich allows fluoride ions to be detected in optically lowc oncentrations.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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