Thermochemical properties of phosphorus compounds

Hartley, Suzanne; Holmes, W. S.; Jacques, J. K.; Mole, M. F.; McCoubrey, J. C.

doi:10.1039/qr9631700204

Cited by 98 publications

(27 citation statements)

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“…The calculated PE bond energies for oxygen and sulfur compare well with the experimental estimates obtained for Me3P0 (32), and Pr3PS (32), respectively. The overall phosphorus~halcogen bond energy is predicted to decrease down the group (Table 1).…”

Section: Resultssupporting

confidence: 71%

A density functional study of the bonding in tertiary phosphine chalcogenides and related molecules

Sandblom¹,

Ziegler²,

Chivers³

1996

Can. J. Chem.

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The nature of the phosphorus-tellurium bond in tertiary phosphine tellurides is not well understood. There is also controversy over the nature of multiple bonding in the lighter chalcogenides and the related ylides and imides. Density functional theory (DFT) was used to investigate the interactions in the molecule, Me3PE (E = 0 , S, Se, Te, BH,, CH,, NH). The calculated PE bond energies and orbital populations reveal contributions from both u donation from the phosphine and T back-donation to the phosphine in all of the above cases. Down the group from oxygen to tellurium, the PE bond weakens from 544 kJ mol-' to 184 kJ mol-I, but multiple bonding becomes more significant with respect to the single bond. For E = BH,, the PB bond energy is 166 kJ mol-'. Trimethylphosphine ylide was found to have a T-bond order of 0.5, while that of trimethylphosphine imine is 0.6. For comparison, the oxides of trimethylamine and trimethylarsine were also calculated to examine the pnictogen4xygen bond; Me,N does not participate in multiple bonding with oxygen, while the T-bond orders for Me3P0 and Me3As0 were calculated as 0.7 and 0.6, respectively.Key words: phosphine chalcogenides, phosphine ylides, phosphine imides, DFT calculations Resume : La nature de la liaison phosphore-tellure dans les tellurures de phosphine tertiaires n'est pas trks bien comprise. I1 ya a Cgalement une controverse relativement la nature de la liaison multiple dans les chalcogtnures plus lCgbres et dans les ylures et imides apparentts. On a fait appel la thCorie de la densitt fonctionnelle (TDF) pour ttudier les interactions dans la molCcule de Me,PE (E = 0 , S, Se, BH,, CH,, NH). Les Cnergies de liaison PE calculCes et les populations des orbitales rCvklent des contributions a la fois du transfert u a partir de la phosphine et du transfert en retour T vers la phosphine dans tous les cas cidessus. La liaison PE s'affaiblit lorsqu'on descend dans la famille de l'oxygbne vers le tellure, elle passe de 544 kJ mol-I a 184 kJ mol-I, mais la liaison multiple devient plus significative par rapport a la liaison simple. Pour E = BH,, 1'Cnergie de la liaison PB est de 166kJ mol-I. On a trouvt que l'ylure de la trimCthylphosphine a une liaison T de l'ordre de 0,5, tandis que pour l'imine de la trimkthylphosphine l'ordre est de 0,6. Pour fins de comparaison, on a tgalement calculC les oxydes de la trimCthylamine et de la trimtthylarsine, pour examiner la liaison oxygbne-azote; Le Me,N ne participe pas a la liaison multiple avec l'oxygbne, alors que calcul des ordres de la liaison T pour le Me,PO et le Me3As0 donnent 0,7 e 0,6 respectivement.Mots clks : chalcogCnures de phosphine, ylure de phosphore, imides de phosphine, calculs de TDF.[Traduit par la redaction]

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Section: Resultssupporting

confidence: 71%

A density functional study of the bonding in tertiary phosphine chalcogenides and related molecules

Sandblom¹,

Ziegler²,

Chivers³

1996

Can. J. Chem.

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“…The formation of a bond between phosphorus and the attacking nucleophile leads to five-coordinated phosphorus in the transition state, the structure of which may be represented by a trigonal bipyramid with the axial disposition of the eliminated and introduced groups. This geometry is supported by data for the molecular structures of fivecoordinated phosphorus compounds, in which the axial bonds are longer and weaker than the equatorial bonds 14 ' 15 .…”

Section: H Fundamental Data On the Mechanisms Of The Hydrolysis Of Pmentioning

confidence: 59%

Kinetics of the Hydrolysis of Phosphate Esters

Bel’skii¹

1977

Russ. Chem. Rev.

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The available information about the kinetics of the hydrolysis of phosphate esters in neutral, alkaline, and acidic media is considered and the mechanisms of the hydrolysis of various reactive forms of mono-, di-, and tri-esters are discussed. A systematic account is given of the rate constants, taking into account the type of ester and its reactive form. The bibliography includes 106 references. CONTENTS

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“…Benson's work includes enthalpy group contributions for four groups given in Table , namely C‐(H) 2 (C)(P) (−10 kJ mol −1 ), C‐(H) 2 (C)(PO) (−14 kJ mol −1 ), P‐(C) 3 (29 kJ mol −1 ) and PO‐(C) 3 (−305 kJ mol −1 ) . However, the standard enthalpies of formation used to derive the group contributions for C‐(H) 2 (C)(P) and C‐(H) 2 (C)(PO) were from Hartley et al and, hence, from a compilation that is not entirely empirical . Thus, a comparison between computationally and experimentally derived group contributions is justified only in the case of P‐(C) 3 and PO‐(C) 3 .…”

Section: Resultsmentioning

confidence: 99%

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

et al. 2018

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Composite quantum chemical methods W1X‐1 and CBS‐QB3 are used to calculate the gas phase standard enthalpy of formation, entropy, and heat capacity of 38 phosphines and phosphine oxides for which reliable experimental thermochemical information is limited or simply nonexistent. For alkyl phosphines and phosphine oxides, the W1X‐1, and CBS‐QB3 results are mutually consistent and in excellent agreement with available G3X values and empirical data. In the case of aryl‐substituted species, different computational methods show more variation, with G3X enthalpies being furthest from experimental values. The calculated thermochemical data are subsequently used to determine Benson group additivity contributions for 24 Benson groups and group pairs involving phosphorus, thereby allowing fast and accurate estimations of thermochemical data of many organophosphorus compounds of any complexity. Such data are indispensable, for example, in chemical process design or estimating potential hazards of new chemical compounds. © 2018 Wiley Periodicals, Inc.

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Thermochemical properties of phosphorus compounds

Cited by 98 publications

References 0 publications

A density functional study of the bonding in tertiary phosphine chalcogenides and related molecules

A density functional study of the bonding in tertiary phosphine chalcogenides and related molecules

Kinetics of the Hydrolysis of Phosphate Esters

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

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