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Ring-whizzing in polyene-PtL 2 complexes revisited

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ABSTRACT

Ring-whizzing was investigated by hybrid DFT methods in a number of polyene–Pt(diphosphinylethane) complexes. The polyenes included cyclopropenium+, cyclobutadiene, cyclopentadienyl+, hexafluorobenzene, cycloheptatrienyl+, cyclooctatetraene, octafluorooctatetraene, 6-radialene, pentalene, phenalenium+, naphthalene and octafluoronaphthalene. The HOMO of a d10 ML2 group (with b2 symmetry) interacting with the LUMO of the polyene was used as a model to explain the occurrence of minima and maxima on the potential energy surface.

No MeSH data available.


The important valence orbitals of a d10 ML2 group, 5–7, along with the computed structures of Pt(PH3)2 and Pt(dpe).
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Figure 2: The important valence orbitals of a d10 ML2 group, 5–7, along with the computed structures of Pt(PH3)2 and Pt(dpe).

Mentions: A d10 ML2 fragment possesses a high-lying HOMO, shown by 5 in Fig. 2, which has b2 symmetry and a low-lying LUMO, 6, of a1 symmetry [22]. An energetically favorable reaction path will be one that maximizes the interactions of these orbitals with the orbitals of a coordinated polyene. The lowest occupied polyene π level is fully symmetric and, therefore, 6 can always interact with it. On the other hand, the LUMO in the π system may not always have the correct symmetry to interact with the b2 orbital on ML2 and it is the evolution of this overlap that has an important impact on the reaction path and activation energy. We will also have an occasion to consider a lower lying filled orbital of b1 symmetry, 7.


Ring-whizzing in polyene-PtL 2 complexes revisited
The important valence orbitals of a d10 ML2 group, 5–7, along with the computed structures of Pt(PH3)2 and Pt(dpe).
© Copyright Policy - Beilstein
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC4979650&req=5

Figure 2: The important valence orbitals of a d10 ML2 group, 5–7, along with the computed structures of Pt(PH3)2 and Pt(dpe).
Mentions: A d10 ML2 fragment possesses a high-lying HOMO, shown by 5 in Fig. 2, which has b2 symmetry and a low-lying LUMO, 6, of a1 symmetry [22]. An energetically favorable reaction path will be one that maximizes the interactions of these orbitals with the orbitals of a coordinated polyene. The lowest occupied polyene π level is fully symmetric and, therefore, 6 can always interact with it. On the other hand, the LUMO in the π system may not always have the correct symmetry to interact with the b2 orbital on ML2 and it is the evolution of this overlap that has an important impact on the reaction path and activation energy. We will also have an occasion to consider a lower lying filled orbital of b1 symmetry, 7.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

Ring-whizzing was investigated by hybrid DFT methods in a number of polyene–Pt(diphosphinylethane) complexes. The polyenes included cyclopropenium+, cyclobutadiene, cyclopentadienyl+, hexafluorobenzene, cycloheptatrienyl+, cyclooctatetraene, octafluorooctatetraene, 6-radialene, pentalene, phenalenium+, naphthalene and octafluoronaphthalene. The HOMO of a d10 ML2 group (with b2 symmetry) interacting with the LUMO of the polyene was used as a model to explain the occurrence of minima and maxima on the potential energy surface.

No MeSH data available.