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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 LUMO of the phenalenium cation is given in 44. The structures of the three stationary points found for phenalenium–Pt(dpe)+ along with their relative energies are shown from a top view in 45–47. Again the groups connected to the phosphorus atoms are not shown.
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Figure 13: The LUMO of the phenalenium cation is given in 44. The structures of the three stationary points found for phenalenium–Pt(dpe)+ along with their relative energies are shown from a top view in 45–47. Again the groups connected to the phosphorus atoms are not shown.

Mentions: The situation for phenalenium–Pt(dpe)+ is very similar. The LUMO for phenalenium+ is a rigorously non-bonding MO, 44 in Fig. 13. One expects and finds η3 structures both within and between rings as given by 45 and 46, respectively, with essentially identical relative energies. Experimentally, all known complexes [64–67] are akin to 45. Our calculated barrier of 14.7 kcal/mol via 47 seems a bit too low. The measured barrier in two Pd(tmeda) complexes was 21.4 and 21.6 kcal/mol [66]. No signs of fluxionality was found in a substituted phenalenium–Pt(PPh3)2+ complex [67].


Ring-whizzing in polyene-PtL 2 complexes revisited
The LUMO of the phenalenium cation is given in 44. The structures of the three stationary points found for phenalenium–Pt(dpe)+ along with their relative energies are shown from a top view in 45–47. Again the groups connected to the phosphorus atoms are not shown.
© Copyright Policy - Beilstein
Related In: Results  -  Collection

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

Figure 13: The LUMO of the phenalenium cation is given in 44. The structures of the three stationary points found for phenalenium–Pt(dpe)+ along with their relative energies are shown from a top view in 45–47. Again the groups connected to the phosphorus atoms are not shown.
Mentions: The situation for phenalenium–Pt(dpe)+ is very similar. The LUMO for phenalenium+ is a rigorously non-bonding MO, 44 in Fig. 13. One expects and finds η3 structures both within and between rings as given by 45 and 46, respectively, with essentially identical relative energies. Experimentally, all known complexes [64–67] are akin to 45. Our calculated barrier of 14.7 kcal/mol via 47 seems a bit too low. The measured barrier in two Pd(tmeda) complexes was 21.4 and 21.6 kcal/mol [66]. No signs of fluxionality was found in a substituted phenalenium–Pt(PPh3)2+ complex [67].

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.