Structure and triboluminescence of polymorphs of hexaphenylcarbodiphosphorane

Hardy, Gordon E.; Zink, Jeffrey I.; Kaska, William C.; Baldwin, James C.

doi:10.1021/ja00493a035

Cited by 158 publications

(116 citation statements)

References 3 publications

(5 reference statements)

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“…The C-PPh 3 bond length amounts to 168.8(3) pm while the C-P(O)Ph 2 bond is longer with 171.7(3) pm. The short P-C bond is located between that of C(PPh 3 ) 2 (163.5) [12] and that of the cation (HC{PPh 3 } 2 ) + (mean value of 169.9 pm from about 10 compounds) [7], indicating a decreasing P-C double bond character down the row C(PPh 3 ) 2 > 2 (C-PPh 3 ) > (HC{PPh 3 } 2 ) + > 2 (C-P(O)Ph 2 ) arising from variable backbonding of the occupied p orbital at the ylidic C atom into P-C Ph σ* orbitals [13]. The P-O distance amounts to 148.9(2) pm and is close to that in OPPh 3 (148.3(2) pm) [14].…”

Section: Crystal Structuresmentioning

confidence: 99%

Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species

Petz

Öxler

Aicher

et al. 2010

Zeitschrift anorg allge chemie

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Abstract. The carbodiphosphorane C(PPh 3 ) 2 (1) is easily hydrolyzed from wet air to give the ylide Ph 3 PCHP(O)Ph 2 (2), which forms addition compounds with various Lewis acids to give neutral or cationic compounds. According to pairs of electrons at the central carbon atom and the oxygen atom, respectively, addition compounds with coordination modes A (via oxygen), B (via carbon), and C (via carbon and oxygen) were isolated either as by-products from reactions of Lewis acids with 1 (contaminated with some 2) or directly with 2. The crystal structures and the spectroscopic properties of 2 and of the addition

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Section: Crystal Structuresmentioning

confidence: 99%

Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species

Petz

Öxler

Aicher

et al. 2010

Zeitschrift anorg allge chemie

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“…oder I2 [24]: nur 0,08 Ä von der P I , P2, Se-Ebene ab. Die A b stände P l -C l (1,69(1) Ä) und P 2 -C 1 (1,70(1) Ä) sind gegenüber den Dimensionen der PCP-Brücke in den M odifikationen von 1 geringfügig, aber signifi kant verlängert (1,629(3) Ä -1,635(5) Ä [25,26] ph3ps -® 7 pph3 c 8 a x= I. kel (130,2(4)°) ist dagegen nur unwesentlich verän dert. C 1 weicht nur 0,05 Ä von der durch P 1, P 2 , 11 gebildeten Ebene ab.…”

Section: Ergebnisse Und Diskussionunclassified

“…D er Abstand C l -I I beträgt 2,123(6) Ä. Wie bei 3' wird der Bindungszustand am besten durch Komplexierung des freien E lektronen paares von 1 plausibel gemacht. Die damit einherge hende leichte Bindungsverlängerung der ylidischen P=C -B indungen gegenüber den in "freien" C arbodi phosphoranen gefundenen W erten [25,26,[28][29][30] wurde auch bei der Komplexierung von 1 sowohl mit H +-Ionen [31] wie auch mit Schwermetallen (Cu1) beobachtet [7]. Für den P -C -P-Winkel wird sowohl für 1 [25,26] (siehe auch Lit.…”

Section: Ergebnisse Und Diskussionunclassified

“…Die damit einherge hende leichte Bindungsverlängerung der ylidischen P=C -B indungen gegenüber den in "freien" C arbodi phosphoranen gefundenen W erten [25,26,[28][29][30] wurde auch bei der Komplexierung von 1 sowohl mit H +-Ionen [31] wie auch mit Schwermetallen (Cu1) beobachtet [7]. Für den P -C -P-Winkel wird sowohl für 1 [25,26] (siehe auch Lit. [28][29][30]) wie für seine A ddukte [7,31] eine gewisse Variationsbreite festge stellt, die durch Packungseffekte mitbedingt sein sollte.…”

Section: Ergebnisse Und Diskussionunclassified

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Addition der schweren Chalkogen-Atome und Halogenonium-Ionen an Carbodiphosphorane / Addition of the Heavy Chalkogen Atoms and Halogenonium Ions to Carbodiphosphoranes

Schmidbaur

Zybill

Neugebauer

et al. 1985

Zeitschrift Für Naturforschung B

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Hexaphenylcarbodiphosphorane Ph3P=C=PPh3 (1) forms deeply coloured, crystalline 1:1 ad- ducts with elemental sulfur, selenium and tellurium (2, 3 and 7, respectively). A superior method of synthesis for 7 is the reaction of Na2Te with (Ph3P)2CCl⊕Cl⊖. All three compounds are thermally unstable and decompose at or below room temperature. A selenium adduct 5 was also obtained with Me3P = C = PPh, (4). The compounds 2 and 3 can be alkylated at the chalkogen atoms using MeOSO2F or PhCH2Cl. Oxydation of 3 leads to Se - Se coupling.Addition of elemental iodine to 1 in molar ratios 1:1. 2:3 and 1:2 affords salt-like products composed of the (Ph2P)2Cl⊕ cation associated with I⊖ and/or I3⊖ anions (8a-c).The crystal and molecular structures of 3 and 8b have been determined by single crystal X-ray diffraction. 3′, containing one half equivalent of disordered tetrahydrofuran, crystallizes in the monoclinic space group P21/n (a = 10.848(6), b = 17.433(8). c = 16.848(9) Å, β = 91.51(5)°. V = 3185.07 Å3, ϱx = 1359 gcm-3, Z = 4). Based on 3488 structure factors, the final R value was 0.103. The selenium is attached to the ylidic carbon atom without major changes of the Ph3P=C=PPh3 skeleton (C - Se = 1.99 Å). 8b crystallizes in the triclinic space group P1̄ (a = 9.935(2). b = 11.507(2), c = 16.646(3) Å, α = 90.91(1), β = 112.00(1), γ = 96.60(1)°, V = 1749.15 A3, ϱx = 1.741 gcm-3, Z = 2). Refinement of 382 parameters on 5096 structure factors converged at R = 0.043. The molecular structure shows close similarities to the selenium adduct 3 (C-I = 2.12 Å).

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“…An X-ray determination of another crystal modification [9] gave a P-C-P angle of 134.4° at room temperature and 131.7° at -160 °C. Finally, it was concluded from an electron diffraction study [10 a] of hexamethylcarbodiphosphorane that there was rapid inversion in the molecule giving an average linear structure, and a recent structure of (Ph2MeP)2C has given an even smaller P-C-P angle of 121.…”

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confidence: 99%

A Study of the Bonding and Geometry in Phosphacumulene Ylides

Albright

Hofmann

Rossi

1980

Zeitschrift Für Naturforschung B

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A series of ab initio molecular orbital calculations have been carried out on phosphacumulene ylides of the type H3P = C = C = X where X = S, O, CNH, and (OH)2. The variation in the P-C-C bond angle was examined and compared to the experimentally determined structures of analogs. The dominant factor in setting the P-C-C angle was found to be the relative π-acceptor capability of the C = X fragment in the plane of the bending motion. Quantitative PMO-arguments were constructed for the X = S, O and (OH)2 cases along this line. It is also shown, that P-C σ* character mixes into the highest occupied molecular orbital. The magnitude of this effect is dictated by the amount of bending and this strongly influences the 1JP-C nuclear spin coupling constants. Finally, the bending in H3P = C = PH3 was also investigated in a similar manner.

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Structure and triboluminescence of polymorphs of hexaphenylcarbodiphosphorane

Cited by 158 publications

References 3 publications

Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species

Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species

Addition der schweren Chalkogen-Atome und Halogenonium-Ionen an Carbodiphosphorane / Addition of the Heavy Chalkogen Atoms and Halogenonium Ions to Carbodiphosphoranes

A Study of the Bonding and Geometry in Phosphacumulene Ylides

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Structure and triboluminescence of polymorphs of hexaphenylcarbodiphosphorane

Cited by 158 publications

References 3 publications

Formation and Crystal Structures of Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species

Formation and Crystal Structures of Lewis Acid Adducts of Ph3PCHP(O)Ph2; New Neutral and Cationic Species

Addition der schweren Chalkogen-Atome und Halogenonium-Ionen an Carbodiphosphorane / Addition of the Heavy Chalkogen Atoms and Halogenonium Ions to Carbodiphosphoranes

A Study of the Bonding and Geometry in Phosphacumulene Ylides

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Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species

Formation and Crystal Structures of Lewis Acid Adducts of Ph₃PCHP(O)Ph₂; New Neutral and Cationic Species