### Abstract

An ab initio SCF geometry optimization on the simple cations {A figure is presented}H_{2}X, with X = F, Cl, NH_{2} and PH_{2} has been performed at the split valence shell (4-31G) level. The computed optimum conformations correspond in each case to a structure in which all atoms lie in the same plane. Comparison of the computed charge distributions reveals that the third period heteroatom (Cl and P) is a better π electron donor than the corresponding second period analogue (F and N). This result parallels that obtained recently [Can. J. Chem. 53, 1144 (1975)] for S and O in {A figure is presented}H_{2}OH and {A figure is presented}H_{2}SH, but contradicts current notions based on assumed values of the C_{π}-X_{π} overlap integrals. It is shown here by explicit calculations of overlap integrals that these assumptions are not always correct. Furthermore, it is shown that arguments based only on overlap are necessarily incomplete since they neglect terms like the energy difference between the interacting orbitals which can play a dominant role. The relative importance of such terms is discussed for these species.

Original language | English |
---|---|

Pages (from-to) | 3085-3088 |

Number of pages | 4 |

Journal | Tetrahedron |

Volume | 31 |

Issue number | 24 |

DOIs | |

Publication status | Published - 1975 |

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### ASJC Scopus subject areas

- Biochemistry
- Organic Chemistry
- Drug Discovery

### Cite this

*Tetrahedron*,

*31*(24), 3085-3088. https://doi.org/10.1016/0040-4020(75)80152-9

**The π-donating ability of heteroatoms in α-substituted methyl cations.** / Bernardi, F.; Csizmadia, I.; Epiotis, N. D.

Research output: Contribution to journal › Article

*Tetrahedron*, vol. 31, no. 24, pp. 3085-3088. https://doi.org/10.1016/0040-4020(75)80152-9

}

TY - JOUR

T1 - The π-donating ability of heteroatoms in α-substituted methyl cations

AU - Bernardi, F.

AU - Csizmadia, I.

AU - Epiotis, N. D.

PY - 1975

Y1 - 1975

N2 - An ab initio SCF geometry optimization on the simple cations {A figure is presented}H2X, with X = F, Cl, NH2 and PH2 has been performed at the split valence shell (4-31G) level. The computed optimum conformations correspond in each case to a structure in which all atoms lie in the same plane. Comparison of the computed charge distributions reveals that the third period heteroatom (Cl and P) is a better π electron donor than the corresponding second period analogue (F and N). This result parallels that obtained recently [Can. J. Chem. 53, 1144 (1975)] for S and O in {A figure is presented}H2OH and {A figure is presented}H2SH, but contradicts current notions based on assumed values of the Cπ-Xπ overlap integrals. It is shown here by explicit calculations of overlap integrals that these assumptions are not always correct. Furthermore, it is shown that arguments based only on overlap are necessarily incomplete since they neglect terms like the energy difference between the interacting orbitals which can play a dominant role. The relative importance of such terms is discussed for these species.

AB - An ab initio SCF geometry optimization on the simple cations {A figure is presented}H2X, with X = F, Cl, NH2 and PH2 has been performed at the split valence shell (4-31G) level. The computed optimum conformations correspond in each case to a structure in which all atoms lie in the same plane. Comparison of the computed charge distributions reveals that the third period heteroatom (Cl and P) is a better π electron donor than the corresponding second period analogue (F and N). This result parallels that obtained recently [Can. J. Chem. 53, 1144 (1975)] for S and O in {A figure is presented}H2OH and {A figure is presented}H2SH, but contradicts current notions based on assumed values of the Cπ-Xπ overlap integrals. It is shown here by explicit calculations of overlap integrals that these assumptions are not always correct. Furthermore, it is shown that arguments based only on overlap are necessarily incomplete since they neglect terms like the energy difference between the interacting orbitals which can play a dominant role. The relative importance of such terms is discussed for these species.

UR - http://www.scopus.com/inward/record.url?scp=0001121924&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001121924&partnerID=8YFLogxK

U2 - 10.1016/0040-4020(75)80152-9

DO - 10.1016/0040-4020(75)80152-9

M3 - Article

VL - 31

SP - 3085

EP - 3088

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 24

ER -