The purpose of the present work is to study the bonding interactions between the substituents and the ring π system for a series of ortho and para MeₙH₃₋ₙM (M = C or Si, n = 0-3) substituted N,N-dimethylaniline . Both ground and excited-state interactions were studied and their magnitudes determined. The experimental data were then used in conjunction with molecular orbital calculations to differentiate among inductive, hyperconjugative, and d-pπ interactions on the ground and excited states. Overall, the study indicates that d orbital involvement in the interactions of organosilicon substituents with unsaturated systems is much less significant than is generally held. The importance of pₛᵢ⁻π and pₛᵢ⁻π* hyperconjugative interactions between silicon σ* orbitals and π system in producing the effects of silicon substitution on unsaturated systems has become more apparent.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc500622 |
| Date | 05 1900 |
| Creators | Jung, Il Nam |
| Contributors | Jones, Paul R., Marshall, James L., 1940-, Brady, William T. |
| Publisher | North Texas State University |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | vii, 134 leaves : ill., Text |
| Rights | Public, Jung, Il Nam, Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved. |
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