Infrared and Raman Spectra of CF<sub>2</sub>N<sub>2</sub>. Evidence for a Diazirine Structure

Bjork, C. W.; Craig, Norman C.; Mitsch, Ronald A.; Overend, John

doi:10.1021/ja01084a007

Cited by 32 publications

(15 citation statements)

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“…In the present paper, we report the derivation of a harmonic force field from vibrational wavenumbers of the parent and the 18 O-substituted isotopic species and from centrifugal distortion constants. 5 Furthermore, we recorded gas electron diffraction (GED) intensities and determined the geometric structure by joint analysis of GED intensities and rotational constants of the parent isotopic species.…”

Section: Introductionmentioning

confidence: 99%

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂

Casper¹,

Christen²,

Mack³

et al. 1996

J. Phys. Chem.

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A harmonic force field for difluorodioxirane was derived from fundamental wavenumbers, isotopic shifts, centrifugal distortion constants, and inertial defect differences. The following geometric structure was determined by a joint analysis of gas electron diffraction intensities and rotational constants of the parent species (rz values with 1σ uncertainties): O−O = 1.578(1), C−O = 1.348(8), C−F = 1.317(6) Å, ∠FCF = 108.8(7)°. The extremely long O−O bond correlates with the small force constant of 2.94 × 102 N m-1.

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Section: Introductionmentioning

confidence: 99%

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂

Casper¹,

Christen²,

Mack³

et al. 1996

J. Phys. Chem.

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“…Despite this dissociation DFD displays a well-structured spectrum of the ii 'B, +z 'Ai nx* transition (origin near 352 nm) which is symmetry allowed both in one-and two-photon excitation. The combined analysis of the vibrational spectrum [ 2,5] and the one- [ 4,7] and two-photon [ 8 ] electronic spectrum has yielded precise values of all nine fundamental vibrational frequencies in the ground z 'Ai and excited x 'Bi state.…”

Section: Introductionmentioning

confidence: 99%

Doppler-free two-photon spectrum of the 000 band of the Ã1B1←X̃1A1 transition in difluorodiazirine, F2CN2

Sieber

Riedle

Neusser

1990

Chemical Physics Letters

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The Doppler-free two-photon excitation spectrum of the vibrationless A 'Btc jt 'A, transition of difluorodiaxirine (F&N,) has been recorded with a resolution of 15 MHz using a cw single-mode dye laser coupled to an external concentric resonator. The asymmetric rotor spectrum has been analysed and more than 350 lines randomly selected from all five branches were assigned in order to fit the ground-and excited-state rotational and quartic centrifugal distortion constants. From the rotational constants the r,.,,., and rvv distances in the ground a 'A, and excited A 'B, state were determined. The geometry change upon excitation is found to be Ar,=3.89 (2) pm and Ar,= -4.09(2) pm. No perturbation in the rotational structure of the 0: band has been found. This points to a small singlet-triplet coupling matrix element in the small molecule limit.

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“…Bjork and coworkers [13] have also reported a set of transferred force constants which, however, lead only to approximate agreement with the observed frequencies. We have therefore reexamined this system and adjusted the force constants such that the average deviations of calculated vibrational frequencies from those observed are within 3.6%.…”

Section: Perjuorodiazirinementioning

confidence: 96%

“…The molecular structure of perfluorodiazirine has been determined by electron diffraction [12], infrared and Raman spectra [13], and the assignment of fundamental frequencies was confirmed from its ultraviolet spectrum [ 141. Bjork and coworkers [13] have also reported a set of transferred force constants which, however, lead only to approximate agreement with the observed frequencies.…”

Section: Perjuorodiazirinementioning

confidence: 99%

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

Tschuikow‐Roux¹,

Jung²

1975

Int J of Chemical Kinetics

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A semiempirical approach has been used to evaluate rate parameters for a three-center decomposition reaction from the point of view of transition state theory, with perfluorodiazirine serving as the prototype molecule. Several activated complex models are considered in which the reaction coordinate is chosen as the 4 N C N bending mode. The consrraints imposed include the principle of concerted bond-order conservation in passing from the initial to the final state, and use is made of empirical bond order-bond length and bond order-force constant relationships. The geometric configuration of the transition state sought is one which conforms with the lowest energy path and is also consistent with the observed entropy of activation. The potential energy of activation is taken as the optimum difference in binding energies (based on the INDO method) between the transition and initial states, and the critical energy is obtained by applying a correction for the zero-point energy difference, derived from normal coordinate analysis. Satisfactory agreement is found in the case of the activated complex model for which the total bond order is conserved and bonds undergoing rupture are assigned a fractional bond order (FBO) of 2 / 3 , derived from the postulate (FBO) = a / B where a ( = 2 ) is the number of bonds breaking, and @( =3) is the number of bonds undergoing change in the ring opening.

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Infrared and Raman Spectra of CF₂N₂. Evidence for a Diazirine Structure

Abstract: butenyllithium at 486 µ is 3.0 X 104, calculated using the extrapolated absorbance maxima. This is in good agreement with that obtained for triphenylmeth-yllithium2 (3.3 X 104) in which decomposition is not a problem.

Cited by 32 publications

References 2 publications

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂

Doppler-free two-photon spectrum of the 000 band of the Ã1B1←X̃1A1 transition in difluorodiazirine, F2CN2

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

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Infrared and Raman Spectra of CF2N2. Evidence for a Diazirine Structure

Abstract: butenyllithium at 486 µ is 3.0 X 104, calculated using the extrapolated absorbance maxima. This is in good agreement with that obtained for triphenylmeth-yllithium2 (3.3 X 104) in which decomposition is not a problem.

Cited by 32 publications

References 2 publications

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF2O2

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF2O2

Doppler-free two-photon spectrum of the 000 band of the Ã1B1←X̃1A1 transition in difluorodiazirine, F2CN2

Model for a three‐center decomposition reaction. I. Perfluorodiazirine

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Infrared and Raman Spectra of CF₂N₂. Evidence for a Diazirine Structure

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂

Electron Diffraction and Vibrational Spectra of Difluorodioxirane, CF₂O₂