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/ange.201610156

Cited by 39 publications

(3 citation statements)

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“…Later, the ambident character of the [PCO] − ion was proven by its reaction with i Pr 3 Si−OTf: At room temperature, this reaction leads predominantly to the O‐silylated kinetic product, i Pr 3 Si−O−C≡P, which then isomerises to the thermodynamically favoured P‐silylated product ( i Pr 3 Si−P=C=O) [50] . A further example for the parallel detection of both possible isomers was achieved using a boryl chloride [(ipc) 2 B−Cl, ipc=diisopinocampheyl] [51] . Although in most cases, the phosphaketene (R−P=C=O) isomers are observed exclusively, oxyphosphaalkynes (R−O−C≡P) have also been accessed, especially with rather oxophilic electrophiles (e. g. in actinide and lanthanide complexes or with boryl electrophiles) [52–55] .…”

Section: Introductionmentioning

confidence: 99%

“…Although in most cases, the phosphaketene (R−P=C=O) isomers are observed exclusively, oxyphosphaalkynes (R−O−C≡P) have also been accessed, especially with rather oxophilic electrophiles (e. g. in actinide and lanthanide complexes or with boryl electrophiles) [52–55] . The S N reactions involving the [PCO] − ion in the initial steps of synthetic processes enabled straightforward access toward a plethora of interesting species representing unique bonding features or electronic structures: the first room‐temperature‐stable singlet phosphinidene, [56] cyaphido‐, [57] and Grignard‐type complexes, [31] as well as a variety of P‐containing heterocycles, [42,49,51,58,59] radicals [43] and biradicaloids [60] …”

Section: Introductionmentioning

confidence: 99%

“… Selected examples for previously reported nucleophilic reactivities of the [PCO] − , [PCS] − and [OCAs] − anions [49–51,64,65] . [(Tr * =4,4’,4’’‐trimethoxytriphenylmethyl), ipc=diisopinocampheyl, Dipp=2,6‐diisopropylphenyl]…”

Section: Introductionmentioning

confidence: 99%

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Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P‐ and As‐Containing Analogues

Horvath

Lőrincz

Benkő

2023

Chemistry A European J

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Although the cyanate and thiocyanate anions belong to the most known textbook examples of ambident nucleophiles, the electronic factors that determine their markedly differing reactivities are still unclear. The recently discovered P-and As-containing [PCX] À and [AsCX] À analogues (X: O, S, Se), whose ambident nature is practically unexplored, may serve as ideal basis for comparison to clarify these differences. This study presents comprehensive theoretical investigations on the nucleophilic behaviours of the whole set of so far known [ECX] À (E: N, P, As, X: O, S, Se) anions, aiming for a systematic understanding of the reactivity patterns and identifying the factors that govern the nucleophilic substitutions. The results indicate that the S N 2 reactions of the O-containing [ECO] À ions are thermodynami-cally preferred at the pnictogen centres E, while the kinetic contributions are only substantial for the N-containing [NCX] À anions. The ambident reactivities of the congeners that contain N or O significantly differ from those with P, As, S, or Se heteroatoms, in line with the inert s-orbital effect, characteristic for the heavier elements. By analysing the electronic structures and bonding patterns of the anions and relevant transition state structures, clear explanations are offered for the differing reactivities of the whole set of [ECX] À anions. To serve for synthetic investigations, possible outcomes of nucleophilic substitutions are predicted, and the target molecules are expected to be versatile and useful synthons.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P‐ and As‐Containing Analogues

Horvath

Lőrincz

Benkő

2023

Chemistry A European J

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HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

et al. 2017

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We describe the isolation and spectroscopic characterization of the heavier phosphorus-containing analogue of isocyanic acid (HPCO), and its isotopologue (DPCO). This fundamental small molecule,which has been postulated to exist in interstellar space,has thus far only been observed at low gas phase concentrations or in inert gas matrices.Inthis report we describe its synthesis,spectroscopic properties,and reactivity in solution. In1830,WçhlerandLiebiginvestigatedcyanicacid(HOCN)and its reactivity towards ammonia in an effort to synthesize ammonium cyanate,w hich was found to afford urea on mild heating.[1] Given the technological limitations at the time, very little was deduced about the constitution of the species studied. However these discoveries were fundamental in defining the concept of isomerism, for example,t he authors discovered that the silver salts of cyanate and fulminate have the same composition. Historic interest in such simple acids has largely focused on fulminic acid (and salts of its conjugate base) in large part due to its explosive properties. [2,3] The molecular structures of isocyanic (HNCO) and fulminic acid (HCNO), were not determined until 1950 by Herzberg and Reid, [4] and 1966 by Beck, respectively.[5] Nowadays,spectroscopic evidence for all four isomeric species isocyanic acid, [6] cyanic acid, [7] fulminic acid, [5] and isofulminic acid is available (Scheme 1).[8] HNCO, [9] HOCN, [10] and HCNO have even been detected in interstellar space. [11] In contrast, analytical data for the heavier phosphoruscontaining homologues HPCO are scarce.Several reports by Matveev claim to have synthesized HOCP from phosphaalkyne precursors, [12,13] however these studies were found to not be reproducible by the group of Becker and others. [14] Becker and co-workers suggested the existence of HOCP after protonation of the 2-phosphaethynolate anion, PCO À , [14,15] but clearly emphasized that this hypothesis was doubtful because the compound could neither be isolated nor further characterized. [16] Numerous theoretical studies have focused on the different isomers of the HPCO system, predicting HPCO to be 23 kcal mol À1 more stable than HOCP,w ith an activation barrier for interconversion of 70 kcal mol À1 . [17][18][19][20][21][22] These computational studies have stimulated further research, indicating that HPCO might be stable in interstellar space.All successful experimental HPCO studies thus far have tried to mimic interstellar conditions,such as low gas-phase concentration of HPCO or the use of noble gas matrices.T hus,t here are two studies of the generation of HPCO by gas discharges of highly dilute PH 3 /CO mixtures (in He or Ar), which allowed the recording of infrared [23] and microwave spectra of HPCO. [24,25] These studies have corroborated the presence of HPCO and not the isomeric HOCP.M ore recently,H PCO has been proposed as an intermediate in the formation of phosphinecarboxamides and phosphinidene-carbene adducts in the reaction of PCO À with ammonium and imidazolium salts, ...

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

Cited by 39 publications

References 67 publications

Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P‐ and As‐Containing Analogues

Deciphering the Differences in Ambident Reactivity between the Cyanate, Thiocyanate Ions, and their P‐ and As‐Containing Analogues

HPCO—A Phosphorus‐Containing Analogue of Isocyanic Acid

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

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