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The fact that the pertinent HOMO-LUMO interactions for the 1,2-silyl migration and decarbonylation mechanisms have destabilizing antibonding components implies that the rearrangements are symmetry-forbidden.
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I is used for reactions in which there is no resonance component.
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A negative ρ value indicates that the reaction site is stabilized by electron-donating substituents.
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18
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The AIMPAC suite of programs is available from Professor R. F. W. Bader, McMaster University, Canada, and from the AIMPAC website (www.chemistry. mcmaster.ca/aimpac).
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20844433461
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Only carbene conformers with the Si-X bond antiperiplanar to the O2-C6 bond were considered in this work.
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49
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20844463683
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note
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NBO only evaluates orbital energies and stabilization energies due to hyperconjugation if a well-defined one-electron effective Hamiltonian operator such as the Fock or Kohn-Sham operator is available. No such operator is available for correlated descriptions such as MP2.
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