The microwave spectrum of 1-fluorophosphaethene, CH2PF

Osman, Osama; Whitaker, Benjamin J.; Simmons, N. P. C.; Walton, D. R. M.; Nixon, John F.; Kroto, Harold W.

doi:10.1016/0022-2852(89)90180-x

Cited by 14 publications

(3 citation statements)

References 15 publications

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“…The CCSD(T) results should be good predictions for these systems and should be of use in the interpretation of experimental data thereon. Partial structures of the XPCH 2 series have been obtained from microwave studies, ,,− and it is likely that the dimethyl derivatives will be subjects of similar studies. Another use of the data is to compare B3LYP results with those from CCSD(T), thereby allowing the assessment of B3LYP for studies of larger phosphaalkenes.…”

Section: Resultsmentioning

confidence: 99%

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Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Watts

Huang

2009

J. Phys. Chem. A

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Ab initio theoretical calculations have been used to study the influence of phosphorus substituents, Y, on the tautomerism between the vinylphosphine XP(H)C(CH(3))=CH(2) and the phosphaalkene XP=C(CH(3))(2) (X = H, F, Cl, Br, OH, and Ar(F); Ar(F) = 2,6-(CF(3))(2)C(6)H(3)) and on the acidity of the aforementioned vinylphosphine. The stabilization of the phosphaalkene and the increased acidity of the vinylphosphine by Ar(F) are possible factors in the successful synthesis of certain isolable phosphaalkenes. In this work, the properties of Ar(F) are assessed theoretically. Density functional theory using the B3LYP functional has been used for all substituents. In addition, coupled-cluster singles and doubles with noniterative triples (CCSD(T)) has been used for X = H, F, Cl, Br, and OH. The phosphaalkene is favored over the vinylphosphine for all substituents, with F having the strongest stabilizing effect. Cl, Br, and OH have stronger stabilizing effects than Ar(F). In contrast, the most acidic vinylphosphine is that with Ar(F). To aid in the interpretation and analysis of future experimental work, CCSD(T) calculations were used to provide structures and vibrational frequencies for the series XP=C(CH(3))(2) (X = H, F, Cl, Br). The influence of the substituent on geometries and C=P and X-P stretching frequencies was examined, and comparisons were made with the CH(2)=PX series.

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Section: Resultsmentioning

confidence: 99%

“… a Microwave data: references (CH 2 PBr); and (CH 2 PH); (CH 2 PF); and (CH 2 PCl). H and H 2 are trans and cis to X, respectively.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Watts

Huang

2009

J. Phys. Chem. A

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“…Although organophosphorus compounds with a double bond between carbon and phosphorus (R′R″CPR) are not common, they are known, being first synthesized by Becker in 1976 . The geometries of the parent compound and some of its halogen derivatives have been described by Kroto and co-workers. − In a recent paper, we asked to what extent such a formally sp 2 -hybridized P atom could participate in a P···P pnicogen bond in complexes (H 2 CPX) 2 , for X = F, Cl, OH, CN, NC, CCH, H, CH 3 , and BH 2 . This study yielded pnicogen bonded complexes with A–P···P–A or A–P···PC approaching a linear arrangement, with A being the atom of X directly bonded to P, and C being the carbon of H 2 CPX.…”

Section: Introductionmentioning

confidence: 99%

Properties of Complexes H₂C═(X)P:PXH₂, for X = F, Cl, OH, CN, NC, CCH, H, CH₃, and BH₂: P···P Pnicogen Bonding at σ-Holes and π-Holes

2013

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Ab initio MP2/aug′-cc-pVTZ calculations have been carried out on complexes H2C(X)P:PXH2, for X = F, Cl, OH, CN, NC, CCH, H, CH3, and BH2. Three sets of complexes have been found on the potential surfaces. Conformation A complexes have A–P···P–A approaching linearity, with A the atom of X directly bonded to P. Conformation B complexes have A–P···P linear, but the P···PC orientation of H2CPX may differ significantly from linearity. Conformation C complexes are unique, since the pnicogen bond involves π-electron donation and acceptance by H2CPX. The order of binding energies of the three conformations of H2C(X)P:PXH2 is C > A > B, with two exceptions. Although the binding energies of conformation C complexes tend to be greater than the corresponding conformation A complexes, intermolecular distances in conformation C tend to be longer than those in conformation A. Charge transfer stabilizes H2C(X)P:PXH2 complexes. The preferred direction of charge transfer is from H2CPX to PXH2. In conformations A and B, charge transfer occurs from a P lone pair on one molecule to an antibonding σ* orbital on the other. However, in conformation C, charge transfer occurs from the π orbital of H2CPX to the σ*P–A orbital of PXH2, and from the lone pair on P of PXH2 through the π-hole to the π*PC orbital of H2CPX. Changes in charges on P upon complexation do not correlate with changes in 31P chemical shieldings. Computed EOM-CCSD spin–spin coupling constants correlate with P–P distances. At each distance, the ordering of 1pJ(P–P) is A > B > C. Binding energies and spin–spin coupling constants of conformation A complexes of (PH2X)2, H2C(X)P:PXH2, and (H2CPX)2 with A–P···P–A approaching linearity have been compared. For complexes with the more electronegative substituents, binding energies are ordered (PH2X)2 > H2C(X)P:PXH2 > (H2CPX)2, while the order is reversed for complexes formed from the more electropositive substituents. A plot of ΔE(PH2X)2/ΔE(H2CPX)2 versus ΔE[H2C(X)P:PXH2]/ΔE(H2CPX)2 indicates that there is a systematic relationship among the stabilities of these complexes. Complexes (PH2X)2 tend to have larger spin–spin coupling constants and shorter P–P distances than H2C(X)P:PXH2, which in turn have larger coupling constants and shorter P–P distances than (H2CPX)2, although there is some overlap. Complexes having similar P–P distances have similar values of 1pJ(P–P).

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Ab initio calculation of NMR shielding in phosphaalkenes X—PCY2

1999

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The microwave spectrum of 1-fluorophosphaethene, CH2PF

Cited by 14 publications

References 15 publications

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Properties of Complexes H₂C═(X)P:PXH₂, for X = F, Cl, OH, CN, NC, CCH, H, CH₃, and BH₂: P···P Pnicogen Bonding at σ-Holes and π-Holes

Ab initio calculation of NMR shielding in phosphaalkenes X—PCY2

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The microwave spectrum of 1-fluorophosphaethene, CH2PF

Cited by 14 publications

References 15 publications

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH3)2(X = H, F, Cl, Br, OH, ArF(ArF= 2,6-(CF3)2C6H3))

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH3)2(X = H, F, Cl, Br, OH, ArF(ArF= 2,6-(CF3)2C6H3))

Properties of Complexes H2C═(X)P:PXH2, for X = F, Cl, OH, CN, NC, CCH, H, CH3, and BH2: P···P Pnicogen Bonding at σ-Holes and π-Holes

Ab initio calculation of NMR shielding in phosphaalkenes X—PCY2

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Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Properties of Complexes H₂C═(X)P:PXH₂, for X = F, Cl, OH, CN, NC, CCH, H, CH₃, and BH₂: P···P Pnicogen Bonding at σ-Holes and π-Holes