Phosphorus Analogues of Diazonium Ions. Stabilities, Spectroscopic Properties, and Electronic Structures of the P Analogues of Methyldiazonium Ion

Rainer Glaser; Christopher J. Horan; Godwin Sik Cheung Choy; Benjamin L. Harris

doi:10.1021/j100188a025

Phosphorus Analogues of Diazonium Ions. Stabilities, Spectroscopic Properties, and Electronic Structures of the P Analogues of Methyldiazonium Ion

Rainer Glaser
, Christopher J. Horan
, Godwin Sik Cheung Choy
, Benjamin L. Harris

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The P analogues of methyldiazonium ion (CH 3 NN) + (1), methyldiphosphonium ion (CH 3 PP) + (2), methylphosphoazonium ion (CH 3 NP) + (3), and methylazophosphonium ion (CH 3 PN) + (4) were studied with ab initio techniques. Potential energy surface analysis shows that the C 3v -symmetric ions all are minima. 4 corresponds to a shallow minimum along the automerization path of its isomer 3. A bridged structure of 2 exists as a local minimum along the automerization path, and this automerization occurs within a tightly bonded ion-molecule complex with small activation barriers. Methyl cation affinities of 43.0, 71.3, 100.4, and 42.1 kcal/mol were determined for the formations of 1-4, respectively, at MP4(fc,sdtq)/6-31 lG(df,p)//MP2- (full)/6-31 lG(df,p) and including MP2(full)/6-31G(d) vibrational zero-point energies. The thermodynamic stabilities of 2 and 3 with regard to the dissociations (CH 3 XY) + → CH 3 + + XY might be affected by exothermic XY oligomerization and the reactions (CH 3 PP) + → CH 3 + + ½P 4 and (CH 3 NP) + → CH 3 + + &frac13;D 3h (PN) 3 were studied. Ions 2 and 3 are predicted to be more stable toward dissociation than 1. These results suggest that 2 and 3 should be detectable in the gas phase and possibly also in superacidic media. Like its aryl analogue, 3 might be accessible synthetically. Spectroscopic properties including IR spectra, dipole and quadrupole moments, rotational constants, and polarizabilities are reported that may assist in their detection. Electronic structures of 1-4 were studied in a variety of ways. A new energy decomposition method related to the definition of the electron density difference function, Δρ = ρ (CH 3 XY + ) - ρ M (CH 3 + ) - ρ M (XY), is presented. Charge distributions in 1-4 are discussed with regard to the Lewis notations. CN- and CP-bonded ions clearly show distinct bonding patterns.

Original language	American English
Journal	Journal of Physical Chemistry
Volume	96
DOIs	https://doi.org/10.1021/j100188a025
State	Published - Apr 1 1992

Disciplines

Chemistry

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@article{b6eadf5297054b698e85a0856b1f39c9,

title = "Phosphorus Analogues of Diazonium Ions. Stabilities, Spectroscopic Properties, and Electronic Structures of the P Analogues of Methyldiazonium Ion",

abstract = " The P analogues of methyldiazonium ion (CH 3 NN) + (1), methyldiphosphonium ion (CH 3 PP) + (2), methylphosphoazonium ion (CH 3 NP) + (3), and methylazophosphonium ion (CH 3 PN) + (4) were studied with ab initio techniques. Potential energy surface analysis shows that the C 3v -symmetric ions all are minima. 4 corresponds to a shallow minimum along the automerization path of its isomer 3. A bridged structure of 2 exists as a local minimum along the automerization path, and this automerization occurs within a tightly bonded ion-molecule complex with small activation barriers. Methyl cation affinities of 43.0, 71.3, 100.4, and 42.1 kcal/mol were determined for the formations of 1-4, respectively, at MP4(fc,sdtq)/6-31 lG(df,p)//MP2- (full)/6-31 lG(df,p) and including MP2(full)/6-31G(d) vibrational zero-point energies. The thermodynamic stabilities of 2 and 3 with regard to the dissociations (CH 3 XY) + \→ CH 3 + + XY might be affected by exothermic XY oligomerization and the reactions (CH 3 PP) + \→ CH 3 + + \½P 4 and (CH 3 NP) + \→ CH 3 + + \&frac13;D 3h (PN) 3 were studied. Ions 2 and 3 are predicted to be more stable toward dissociation than 1. These results suggest that 2 and 3 should be detectable in the gas phase and possibly also in superacidic media. Like its aryl analogue, 3 might be accessible synthetically. Spectroscopic properties including IR spectra, dipole and quadrupole moments, rotational constants, and polarizabilities are reported that may assist in their detection. Electronic structures of 1-4 were studied in a variety of ways. A new energy decomposition method related to the definition of the electron density difference function, \Δ\ρ = \ρ (CH 3 XY + ) - \ρ M (CH 3 + ) - \ρ M (XY), is presented. Charge distributions in 1-4 are discussed with regard to the Lewis notations. CN- and CP-bonded ions clearly show distinct bonding patterns.",

author = "Rainer Glaser and Horan, \{Christopher J.\} and Choy, \{Godwin Sik Cheung\} and Harris, \{Benjamin L.\}",

year = "1992",

month = apr,

day = "1",

doi = "10.1021/j100188a025",

language = "American English",

volume = "96",

journal = "Journal of Physical Chemistry",

}

TY - JOUR

T1 - Phosphorus Analogues of Diazonium Ions. Stabilities, Spectroscopic Properties, and Electronic Structures of the P Analogues of Methyldiazonium Ion

AU - Glaser, Rainer

AU - Horan, Christopher J.

AU - Choy, Godwin Sik Cheung

AU - Harris, Benjamin L.

PY - 1992/4/1

Y1 - 1992/4/1

N2 - The P analogues of methyldiazonium ion (CH 3 NN) + (1), methyldiphosphonium ion (CH 3 PP) + (2), methylphosphoazonium ion (CH 3 NP) + (3), and methylazophosphonium ion (CH 3 PN) + (4) were studied with ab initio techniques. Potential energy surface analysis shows that the C 3v -symmetric ions all are minima. 4 corresponds to a shallow minimum along the automerization path of its isomer 3. A bridged structure of 2 exists as a local minimum along the automerization path, and this automerization occurs within a tightly bonded ion-molecule complex with small activation barriers. Methyl cation affinities of 43.0, 71.3, 100.4, and 42.1 kcal/mol were determined for the formations of 1-4, respectively, at MP4(fc,sdtq)/6-31 lG(df,p)//MP2- (full)/6-31 lG(df,p) and including MP2(full)/6-31G(d) vibrational zero-point energies. The thermodynamic stabilities of 2 and 3 with regard to the dissociations (CH 3 XY) + → CH 3 + + XY might be affected by exothermic XY oligomerization and the reactions (CH 3 PP) + → CH 3 + + ½P 4 and (CH 3 NP) + → CH 3 + + &frac13;D 3h (PN) 3 were studied. Ions 2 and 3 are predicted to be more stable toward dissociation than 1. These results suggest that 2 and 3 should be detectable in the gas phase and possibly also in superacidic media. Like its aryl analogue, 3 might be accessible synthetically. Spectroscopic properties including IR spectra, dipole and quadrupole moments, rotational constants, and polarizabilities are reported that may assist in their detection. Electronic structures of 1-4 were studied in a variety of ways. A new energy decomposition method related to the definition of the electron density difference function, Δρ = ρ (CH 3 XY + ) - ρ M (CH 3 + ) - ρ M (XY), is presented. Charge distributions in 1-4 are discussed with regard to the Lewis notations. CN- and CP-bonded ions clearly show distinct bonding patterns.

AB - The P analogues of methyldiazonium ion (CH 3 NN) + (1), methyldiphosphonium ion (CH 3 PP) + (2), methylphosphoazonium ion (CH 3 NP) + (3), and methylazophosphonium ion (CH 3 PN) + (4) were studied with ab initio techniques. Potential energy surface analysis shows that the C 3v -symmetric ions all are minima. 4 corresponds to a shallow minimum along the automerization path of its isomer 3. A bridged structure of 2 exists as a local minimum along the automerization path, and this automerization occurs within a tightly bonded ion-molecule complex with small activation barriers. Methyl cation affinities of 43.0, 71.3, 100.4, and 42.1 kcal/mol were determined for the formations of 1-4, respectively, at MP4(fc,sdtq)/6-31 lG(df,p)//MP2- (full)/6-31 lG(df,p) and including MP2(full)/6-31G(d) vibrational zero-point energies. The thermodynamic stabilities of 2 and 3 with regard to the dissociations (CH 3 XY) + → CH 3 + + XY might be affected by exothermic XY oligomerization and the reactions (CH 3 PP) + → CH 3 + + ½P 4 and (CH 3 NP) + → CH 3 + + &frac13;D 3h (PN) 3 were studied. Ions 2 and 3 are predicted to be more stable toward dissociation than 1. These results suggest that 2 and 3 should be detectable in the gas phase and possibly also in superacidic media. Like its aryl analogue, 3 might be accessible synthetically. Spectroscopic properties including IR spectra, dipole and quadrupole moments, rotational constants, and polarizabilities are reported that may assist in their detection. Electronic structures of 1-4 were studied in a variety of ways. A new energy decomposition method related to the definition of the electron density difference function, Δρ = ρ (CH 3 XY + ) - ρ M (CH 3 + ) - ρ M (XY), is presented. Charge distributions in 1-4 are discussed with regard to the Lewis notations. CN- and CP-bonded ions clearly show distinct bonding patterns.

UR - https://scholarsmine.mst.edu/chem_facwork/2810

UR - http://doi.org/10.1021/j100188a025

U2 - 10.1021/j100188a025

DO - 10.1021/j100188a025

M3 - Article

VL - 96

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

ER -

Phosphorus Analogues of Diazonium Ions. Stabilities, Spectroscopic Properties, and Electronic Structures of the P Analogues of Methyldiazonium Ion

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