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Issue 12, 1989
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A comparison of semi-empirical and ab initio SCF-MO potential energy surfaces for the reaction of H2C[double bond, length half m-dash]O with R3P[double bond, length half m-dash]CH2 and RP[double bond, length half m-dash]CH2

Abstract

The reaction between HP[double bond, length half m-dash]CH2 and H2C[double bond, length half m-dash]O is predicted at the MNDO, PM3 and 3-21G*ab initio SCF-MO levels to proceed via a non-planar, unsymmetrical and relatively high energy transition state corresponding to a distorted π2s+π2a cycloaddition, in contrast to the planar, symmetrical and lower energy saddle point located for the allowed cycloaddition between H3P[double bond, length half m-dash]CH2 and H2C[double bond, length half m-dash]O. The ‘allowed’ character of the latter reaction is attributed to contributions from the P–H bonds and not to asymmetry in the reactant orbitals or to ionic character in the wavefunction. The methyl analogue Me3P[double bond, length half m-dash]CH2 reveals a less synchronous transition state for cycloaddition, with a significant orbital contribution from the axial P–Me bond in particular.

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Article type: Paper
DOI: 10.1039/P29890002115
Citation: J. Chem. Soc., Perkin Trans. 2, 1989,0, 2115-2119
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    A comparison of semi-empirical and ab initio SCF-MO potential energy surfaces for the reaction of H2C[double bond, length half m-dash]O with R3P[double bond, length half m-dash]CH2 and RP[double bond, length half m-dash]CH2

    H. S. Rzepa, J. Chem. Soc., Perkin Trans. 2, 1989, 0, 2115
    DOI: 10.1039/P29890002115

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