An electron-diffraction investigation of the molecular structure and thermal dissociation of gaseous PCl5 at 90°C

McClelland, Bruce W.; Hedberg, Lise; Hedberg, Kenneth

doi:10.1016/0022-2860(83)90034-0

Cited by 14 publications

(11 citation statements)

References 12 publications

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“…However, the r g structures of both phosphoranes as well as the r α and r a structures of PCl 5 are known from gas electron diffraction studies. 29−31 The experimental 29,30 r g and r α internuclear distances are listed in Table 5. Like PH 3 F 2 and PF 5 (see subsection 3.3), PCl 3 F 2 and PCl 5 form trigonal bipyramidal molecules of D 3 h point-group symmetry in the gas phase.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Using the theoretical best estimate of the r e structure of PCl 3 F 2 , the rotational constants of P 35 In PCl 5 , the bond lengths at equilibrium (best estimates) are distinctly shorter than the corresponding r g distances, 30 by 1.0 and 0.9 pm, respectively, for the equatorial and axial bonds. These differences correspond to at least three times the experimental 30 uncertainties (see Table 5), which appears to be quite substantial.…”

Section: The Journal Of Physical Chemistry Amentioning

confidence: 99%

“…29 Finally, for PCl 5 average structural parameters denoted r α , r g , and r a are available. 30,31…”

Section: Introductionmentioning

confidence: 99%

“…29 Finally, for PCl 5 average structural parameters denoted r α , r g , and r a are available. 30,31 Previously, we considered target and test molecules consisting only of first-row and hydrogen atoms. 21 We start our current investigation by demonstrating that the chosen computational procedure is capable of accurately describing also the geometries of selected test molecules containing second-row atoms (P and Cl), namely, PH (X 3 Σ − ), PF (X 3 Σ − ), PCl (X 3 Σ − ), PH 2 (X 2 B 1 ), PF 2 (X 2 B 1 ), and PH 3 (X 1 A 1 ).…”

Section: Introductionmentioning

confidence: 99%

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Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Breidung

Thiel

2019

J. Phys. Chem. A

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Among the title species, a reliable and accurate equilibrium geometry (re structure) is available only for PF3, which has been determined experimentally more than 20 years ago. Here, we report accurate re structures for all title molecules, which were obtained using a composite computational approach based on explicitly correlated coupled-cluster theory (CCSD(T)-F12b) in conjunction with a large correlation-consistent basis set (cc-pCVQZ-F12) to take core–valence electron correlation into account. Additional terms were included to correct for the effects of iterative triple excitations (CCSDT), noniterative quadruple excitations (CCSDT(Q)), and scalar relativistic contributions (DKH2-CCSD(T)). The performance of this computational procedure was established through test calculations on selected small molecules (PH, PF, PCl, PH2, PF2, and PH3). For PF3, PCl3, PH3F2, and PF5 sufficiently accurate experimental ground-state rotational constants from the literature were used to determine semiexperimental re structures, which were found to be in excellent agreement with the corresponding best estimates from the current composite approach. The recommended equilibrium structural parameters are for PCl3, re(PCl) = 203.94 pm and θe(ClPCl) = 100.18°; for PH3F2, re(PHeq) = 138.38 pm and re(PFax) = 164.15 pm; for PF5, re(PFeq) = 153.10 pm and re(PFax) = 157.14 pm; for PCl3F2, re(PCleq) = 200.21 pm and re(PFax) = 159.37 pm; and for PCl5, re(PCleq) = 201.29 pm and re(PClax) = 211.83 pm. The associated uncertainties are estimated to be ±0.10 pm and ±0.10°, respectively.

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Section: Results and Discussionmentioning

confidence: 99%

Section: The Journal Of Physical Chemistry Amentioning

confidence: 99%

“…29 Finally, for PCl 5 average structural parameters denoted r α , r g , and r a are available. 30,31…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Breidung

Thiel

2019

J. Phys. Chem. A

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“…Furthermore, the difference in the lengths of axial and equatorial bonds, Δ r = r (MX ax ) − r (MX eq ), depends strongly on whether M is a Group 5 or a Group 15 element. In the former case, values of Δ r are found in the range 0.00–0.05 Å, whereas in the latter Δ r spans the range 0.05–0.10 Å, the last value representing a 5 % difference (in the PCl bonds of PCl 5 45). This familiar behavior of the Group 15 derivatives has been rationalized in terms of the effective electronegativity of the central atom and the hypervalent nature and consequent orbital deficiency of the molecule, implying a significant difference in polarity between axial and equatorial MX bonds 46.…”

Section: Resultsmentioning

confidence: 93%

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂

McGrady

Haaland

Verne

et al. 2005

Chemistry A European J

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The molecular structures of the monomeric, pentacoordinated methylchloroniobium(V) compounds Me 3 NbCl 2 and Me 2 NbCl 3 have been determined by gas electron diffraction (GED) and Density Functional Theory (DFT) calculations, and, for Me 3 NbCl 2 , by single crystal X-ray diffraction. Each of the molecules is found to have a heavy-atom skeleton in the form of a trigonal bipyramid (TBP) with Cl atoms in the axial positions, in accord with their vibrational spectra. The TBP is somewhat distorted in the case of Me 2 NbCl 3 with the two axial Nb-Cl bonds bent away from the equatorial, slightly shorter Nb-Cl bond. In the case of Me 3 NbCl 2 , moreover, the X-ray model suggests structural distortions away from the idealized C 3h geometry, in line with the results of quantum

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A systematic ab initio study of the group V trihalides MX₃ and pentahalides MX₅ (M = PBi, X = FI)

Breidung

Thiel

1992

J Comput Chem

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Ab initio calculations using effective core potentials and polarized split-valence basis sets are reported for the title compounds. The calculated geometries, vibrational frequencies, infrared intensities, harmonic force fields, dipole moments, relative energies, and barriers to pseudorotation are compared with the available experimental data for the known molecules. Predictions are made for those pentahalides that are still unknown. Trends in the calculated properties are identified and discussed.

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An electron-diffraction investigation of the molecular structure and thermal dissociation of gaseous PCl5 at 90°C

Cited by 14 publications

References 12 publications

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂

A systematic ab initio study of the group V trihalides MX₃ and pentahalides MX₅ (M = PBi, X = FI)

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An electron-diffraction investigation of the molecular structure and thermal dissociation of gaseous PCl5 at 90°C

Cited by 14 publications

References 12 publications

Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5

Equilibrium Structures of the Phosphorus Trihalides PF3 and PCl3, and the Phosphoranes PH3F2, PF5, PCl3F2, and PCl5

Valence Shell Charge Concentrations at Pentacoordinate d0Transition‐Metal Centers: Non‐VSEPR Structures of Me2NbCl3and Me3NbCl2

A systematic ab initio study of the group V trihalides MX3 and pentahalides MX5 (M = PBi, X = FI)

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Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Equilibrium Structures of the Phosphorus Trihalides PF₃ and PCl₃, and the Phosphoranes PH₃F₂, PF₅, PCl₃F₂, and PCl₅

Valence Shell Charge Concentrations at Pentacoordinate d⁰Transition‐Metal Centers: Non‐VSEPR Structures of Me₂NbCl₃and Me₃NbCl₂

A systematic ab initio study of the group V trihalides MX₃ and pentahalides MX₅ (M = PBi, X = FI)