Synthesis, Structure and Bonding Properties of 3-Phosphoindoles Analogues of Group 15

Mazières, Marie‐Rose; Rauzy, K.; Bellan, J.; Sanchez, M.; Pfister‐Guillouzo, G.; Senio, A.

doi:10.1080/10426509308032354

Cited by 23 publications

(21 citation statements)

References 3 publications

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“…Both fall well within the range of known P=As double‐bonded species (cf. Mes*‐P=As‐Cp* 536.8, Mes*‐P=As‐Mes* 524.5, (AsPNMes*)Nb(N[Np]Ar) 3 +349 with Np=CH 2 t Bu and Ar=3,5‐C 6 H 3 Me 2 , 1H ‐1‐aza‐3‐phospha‐2‐arsa‐indene 315 ppm) . In contrast, the resonance of 2 is a broad singlet at +5.4 ppm (Δ ν 1/2 =99 Hz; cf.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Hinz

Schulz

Villinger

2016

Chemistry A European J

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The synthesis of a molecule containing four adjacent different pnictogens was attempted by conversion of a Group 15 allyl analogue anion [Mes*NAsPMes*](-) (Mes*=2,4,6-tri-tert-butylphenyl) with antimony(III) chloride. A suitable precursor is Mes*N(H)AsPMes* (1) for which several syntheses were investigated. The anions afforded by deprotonation of Mes*N(H)AsPMes* were found to be labile and, therefore, salts could not be isolated. However, the in situ generated anions could be quenched with SbCl3 , yielding Mes*N(SbCl2 )AsPMes* (4).

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Section: Methodsmentioning

confidence: 99%

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Hinz

Schulz

Villinger

2016

Chemistry A European J

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“…As dominant species we identified 3P [( R , S ) isomer, +134.5 ( J PH = 18 Hz, J PH = 10 Hz), −52.5 ( 1 J PP = 192 Hz, 1 J PH = 203 Hz, 2 J PH = 10.4 Hz); ( R , R ) isomer +131.5 ( J PH = 21 Hz, J PH = 10 Hz), −27.1 ( 1 J PP = 250 Hz, 1 J PH = 223 Hz, 2 J PH = 10.4 Hz)] besides several other side products, e.g., the amino-diphosphene Ter–PP–N(H)–Ter [+480.2, +306.5 ppm; 1 J PP = 546 Hz, 2 J PH = 10.4 Hz; cf. Ter–PP–Mes*, +526.2, 455.5 ppm; 1 J PP = 572 Hz; Mes*N(H)PPMes*, +316.2, +450.0 ppm, 1 J PP = 532 Hz, 2 J PH = 8.4 Hz] − and TerPH 2 (−147.1 ppm). Because no pure product could be isolated from the reaction mixtures, this reaction pathway was not further pursued (vide infra metathesis reaction).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Heavy Cyclodipnictadiphosphanes [ClE(μ-P-Ter)]₂ [E = P, As, Sb, or Bi; Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl]

2016

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A complete series of terphenyl-substituted 1,3-dichloro-1,3-dipnicta-2,4-diphosphanes {[ClE(μ-P-Ter)]2, where E = P, As, Sb, or Bi and Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl} was prepared and fully characterized. While the heavy derivatives with E = Sb or Bi can be accessed via conversion of silylated phosphanes with amino-dichloropnictanes and subsequent elimination of TerNH2, the lighter congeners could be prepared only by a metathesis reaction of [ClBi(μ-P-Ter)]2 with PCl3 and AsCl3. Spectroscopic and structural data indicate the existence of cis and trans isomers of [ClP(μ-P-Ter)]2 in contrast to all heavier derivatives, for which only the trans isomer was obtained.

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“…Hydrogen atoms and solvent molecules are omitted for clarity;i n(a), only the coordinating oxygen atoms of DME are shown. Interatomic distances []: a) Na[1a]: P1-P2 2.1216 (12), P2-C2 1.725(4), C2-N1 1.405(4), N1-C1 1.407(4), C1-O1 1.268(3), C1-P1 1.760(3), C2-C3 1.421(5), C3-C4 1.352(6), C4-C5 1.420(6), C5-C6 1.351(5), C6-N1 1.395(4);b)Na[1b]: P1-P2 2.1154-(17), P2-C2 1.722(5), C2-N1 1.406(5), N1-C1 1.435(5), C1-O1 1.245-(5), C1-P1 1.782(5), C2-C3 1.415(6), C3-C4 1.341(6), C4-C5 1.426(6), C5-C6 1.418(6), C6-N1 1.428(5), C5-C7 1.395(6), C7-C8 1.369(6), C8-C9 1.385(7), C9-C10 1.376(6), C10-C6 1.407(6);c)Si[1b]: P1-P2 2.1038(7), P2-C2 1.7274 (19),C 2-N1 1.406(2), N1-C1 1.386(2), C1-O1 1.341 (2), C1-P1 1.7344 (18), C2-C3 1.425 (3), C3-C4 1.342 (3), C4-C5 1.432 (3), C5-C6 1.416 (2), C6-N1 1.440 (2), C5-C7 1.401 (3), C7-C8 1.368 (3), C8-C9 1.387 (3), C9-C10 1.384 (3), C10-C6 1.395 (3).…”

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confidence: 94%

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.Numerous p-conjugated molecules have astrong impact in the studies of new organic semiconductors and materials,such as dyes in lasers, [1] sensors,l ight emitting diodes, [2] and components for solar cells.[3] Introduction of main group elements in the extended p-systems such as sulfur, [4] boron, [5] silicon, [6] arsenic, [7] and phosphorus [8] allow the physical and electronic properties to be tuned.[9] Unsaturated molecules with low-valent s 2 ,l 3 -phosphorus centers have at endencyt o oligomerize and/or form cage-compounds,l imiting their application.[10] But several successful attempts to use R 2 C= PR and RCPm onomers for the synthesis of conjugated polymers were reported. [11] Compared to the C = C p-bond, the P = Cdouble bond is significantly weaker and the gap between the p (HOMO) and p*(LUMO) orbitals of the C = Pb ond is much smaller. [9g, 12] Phosphorus-containing p-conjugated heterocycles are often easier to handle, [8] and sodium phosphaethynolate,N a(OCP), proved to be av ersatile building block for those (see selected examples in Scheme 1). )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. [19] These new compounds may find applications in electronic devices or chemical sensors.We first further improved the synthesis of Na(OCP), which can now be very easily prepared on aseveral-hundred gram scale in high yield by simply exposing as olution of NaOtBu and dimethylcarbonate in THF to PH 3 (Scheme 2).[20] Subsequently,N a(OCP) was reacted with various 2...

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Synthesis, Structure and Bonding Properties of 3-Phosphoindoles Analogues of Group 15

Cited by 23 publications

References 3 publications

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Synthesis of Heavy Cyclodipnictadiphosphanes [ClE(μ-P-Ter)]₂ [E = P, As, Sb, or Bi; Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl]

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

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Synthesis, Structure and Bonding Properties of 3-Phosphoindoles Analogues of Group 15

Cited by 23 publications

References 3 publications

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Synthesis of a Molecule with Four Different Adjacent Pnictogens

Synthesis of Heavy Cyclodipnictadiphosphanes [ClE(μ-P-Ter)]2 [E = P, As, Sb, or Bi; Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl]

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

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Synthesis of Heavy Cyclodipnictadiphosphanes [ClE(μ-P-Ter)]₂ [E = P, As, Sb, or Bi; Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl]