2002
DOI: 10.1021/jp025958q
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The Bonding Nature of Some Simple Sigmatropic Transition States from the Topological Analysis of the Electron Localization Function

Abstract: It is shown that the topological analysis of the electron localization function (ELF), a measure of the local Pauli repulsion, is a useful tool to describe the bonding nature of transition structures of simple pericyclic processes. In this work, we have revisited the [1s,3a]hydrogen, [1a,3s]methyl, and [1a,3s]fluorine simple sigmatropic rearrangements in the allyl system. Results based on the integrated densities over the ELF basins and their related properties at the B3LYP/6-311++G(d,p) level of theory showed… Show more

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Cited by 21 publications
(18 citation statements)
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References 68 publications
(144 reference statements)
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“…It is worth mentioning that the V(C1,H6,C5) trisynaptic basin present in P4 ‐ 4 becomes two V(C1) and V(C5) monosynaptic basins, related to two C1 and C5 pseudoradical centres, and one V(H1) monosynaptic basin, related to a free hydrogen nucleus, at the MPWB1K/6‐31G(d) level (see Figure S3 in Supporting Information). Note that a similar non‐bonding pattern was found in the TS associated with the [1,3] sigmatropic rearrangement of propene ( 8 ) at the B3LYP/6‐311++G(d,p) level …”
Section: Resultssupporting
confidence: 65%
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“…It is worth mentioning that the V(C1,H6,C5) trisynaptic basin present in P4 ‐ 4 becomes two V(C1) and V(C5) monosynaptic basins, related to two C1 and C5 pseudoradical centres, and one V(H1) monosynaptic basin, related to a free hydrogen nucleus, at the MPWB1K/6‐31G(d) level (see Figure S3 in Supporting Information). Note that a similar non‐bonding pattern was found in the TS associated with the [1,3] sigmatropic rearrangement of propene ( 8 ) at the B3LYP/6‐311++G(d,p) level …”
Section: Resultssupporting
confidence: 65%
“…Note that a similar non-bonding pattern was found in the TS associated with the [1,3] sigmatropic rearrangement of propene (8) at the B3LYP/6-311++G(d,p) level. [37]…”
Section: ) Groupmentioning
confidence: 99%
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“…14 Because we are more interested here in exploring the reaction mechanism topologies at pericyclic and pseudopericyclic transition structures, we have resorted to the ELF picture of bonding. Previous work on benchmark pericyclic reactions corresponding to the ͓1 s ,3 a ͔-hydrogen, ͓1 a ,3 s ͔-methyl, and ͓1 a ,3 s ͔-fluorine 16 sigmatropic shifts in the allyl system have emphasized the usefulness of the analysis of properties of the electron density, integrated over the ELF basins, to obtain a clear picture of electronic rearrangement which is complementary to the traditionally used Woodward-Hoffmann analysis. We present here the first results from an ongoing systematic study concerning the characterization of bonding at pericyclic and pseudopericyclic transition states using the ELF analysis.…”
Section: Introductionmentioning
confidence: 99%