Gauche effect and PM3 calculation of open-chain polyphosphorus hydrides

Ding, Feng; Zhang, Liangfu

doi:10.1002/(sici)1097-461x(1996)60:5<1037::aid-qua10>3.0.co;2-4

Cited by 4 publications

(4 citation statements)

References 11 publications

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“…21,23,24,25 Very recent investigations focused mainly on the thermochemic properties of H 2 PPH 2 and its cation, 26,27 and the gauche effect in this system. 28 However, the theoretical level of the calculations was usually lower than that used in the earlier Ref. 25.…”

Section: Introductionmentioning

confidence: 91%

Theoretical study of the dipole-bound anion (HPPH3)−

Skurski¹,

Gutowski²,

Simons³

1999

The Journal of Chemical Physics

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A theoretical prediction on intermolecular monoelectron dihydrogen bond H e H in the cluster anion ( FH ) 2 {e}( HF ) 2The possibility of electron binding to the HPPH 3 and H 2 PPH 2 tautomers of diphosphine was studied at the coupled cluster level of theory with single, double, and noniterative triple excitations. The HPPH 3 tautomer, with a dipole moment of 3.7 D, binds an electron by 333 cm Ϫ1 , whereas the H 2 PPH 2 tautomer forms neither a dipole-nor valence-bound anionic state. It is suggested that the HPPH 3 tautomer, which is kinetically stable but thermodynamically unstable relative to H 2 PPH 2 , may be formed by photodetachment from the P 2 H 4 Ϫ species examined in this work. An unusual aspect of the (HPPH 3 ) Ϫ anion is that electron correlation contributes 82% to the electronic stability and effects beyond the fourth order of the Mo "ller-Plesset perturbation theory contribute 55%.

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Section: Introductionmentioning

confidence: 91%

Theoretical study of the dipole-bound anion (HPPH3)−

Skurski¹,

Gutowski²,

Simons³

1999

The Journal of Chemical Physics

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“…Simple pentacoordinated phosphorus compounds such as the hypothetical PH 5 and PH 3 F 2 species, PF 5 , or cyclic pentaoxyphosphoranes have been extensively studied with high-level ab initio theory. − Their structures and the mechanisms associated with their intramolecular rearrangement processes have been examined. For PH 5 , Kutzelnigg and Wasilewski demonstrated that the ground state is a TBP structure ( D 3 h ) that undergoes a Berry pseudorotation process via a square-pyramidal ( C 4 v ) transition state, with an energetic barrier of about 2 kcal/mol …”

Section: Resultsmentioning

confidence: 99%

Diastereoselectivity of Borane Addition to Chiral Triquinphosphoranes. NMR, X-ray, and Molecular Modeling Studies

Marchi¹,

Fotiadu²,

Buono³

1999

Organometallics

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Series of new chiral tricyclic pentacoordinated phosphorus compounds, “triquinphosphoranes” (13 − 18, 21, 22, and 24), were prepared from chiral enantiopure diamino diols that present a C 2 symmetry axis. 31P and 13C NMR data are consistent either with a low-energy single-step Berry pseudorotation process between the two possible diastereomeric trigonal-bipyramidal structures TBP(R P) and TBP(S P) or with the chiral square-pyramidal structure SP. Triquinphosphoranes reacted with borane to give two stable monoadducts with opposite configurations at the phosphorus center which do not undergo epimerization. The diastereoselectivity of this reaction depends strongly on the nature and the position of the substituents, the highest diastereomeric excesses being obtained with 4,9-diisopropyl (28; 90% de) and 4,9-diisobutyl (29; 86% de) compounds. The X-ray structure of the major diastereomer 28M revealed that it is remarkably close to an ideal TBP, exhibiting an S P absolute configuration. Semiempirical AM1 MO calculations predict that TBP(R P) and TBP(S P) ground-state species are in rapid equilibrium through a SP transition state, the activation barrier being about 5 kcal/mol. Calculations predict a marked predominance of the R P form in all cases, except for 6,7-diPh triquinphosphorane 22. Steric interactions between the substituents and the tricyclic phosphorane skeleton explain the prevalence of one diastereomer. The diastereoselectivity observed in borane addition on 15 is rationalized in terms of a kinetically controlled process in which the minor triquinphosphorane diastereomer reacts faster than the major one to afford (S P)-28M.

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“…Also the embedding of H‐terminated tetraphosphane units into bicyclic systems improves their thermal stability which allowed the first crystal structure determinations for such compounds 16. 17 The rigid geometry in such bicyclic systems ensures that the phosphorus lone pairs of neighboring atoms adopt the more stable gauche conformation 18. 19 Herein, we report synthesis, structure and stereochemical aspects of a stable ferrocenylene bridged H‐terminated tetraphosphane oxide ( 1 ), which is only the second diphospha[2]ferrocenophane as well as the first monooxidized tetraphosphane reported so far.…”

Section: Methodsmentioning

confidence: 99%

“…[16,17] The rigid geometry in such bicyclic systems ensures that the phosphorus lone pairs of neighboring atoms adopt the more stable gauche conformation. [18,19] Herein, we report synthesis, structure and stereochemical aspects of a stable ferrocenylene bridged H-terminated tetraphosphane oxide (1), which is only the second diphospha [2]ferrocenophane as well as the first monooxidized tetraphosphane reported so far.…”

mentioning

confidence: 99%

Diphospha[2]ferrocenophane (alias 1,4‐Dihydrotetraphosphaneoxide): Stereoselective Formation via Hydrolytic PP Bond Formation

Moser

Belaj

Pietschnig

2009

Chemistry A European J

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Connected by water: Water, which usually cleaves the PP bond in diphosphenes, can also be used for PP bond formation. This has been demonstrated for a metallocene‐bridged bisdiphosphene with both PP units in the proximity. The resulting ferrocenophane contains an H‐terminated linear P4 chain (see scheme) for which only a limited number of stereoisomers is observed owing to structural restraints.

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Gauche effect and PM3 calculation of open-chain polyphosphorus hydrides

Cited by 4 publications

References 11 publications

Theoretical study of the dipole-bound anion (HPPH3)−

Theoretical study of the dipole-bound anion (HPPH3)−

Diastereoselectivity of Borane Addition to Chiral Triquinphosphoranes. NMR, X-ray, and Molecular Modeling Studies

Diphospha[2]ferrocenophane (alias 1,4‐Dihydrotetraphosphaneoxide): Stereoselective Formation via Hydrolytic PP Bond Formation

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