Noncovalent Dimerization after Enediyne Cyclization on Au(111).

@article{deOteyza2016NoncovalentDA,
  title={Noncovalent Dimerization after Enediyne Cyclization on Au(111).},
  author={Dimas G. de Oteyza and Alejandro P{\'e}rez Paz and Yen-Chia Chen and Zahra Pedramrazi and Alexander Riss and Sebastian Wickenburg and Hsin-Zon Tsai and Felix R. Fischer and Michael F. Crommie and {\'A}ngel Rubio},
  journal={Journal of the American Chemical Society},
  year={2016},
  volume={138 34},
  pages={
          10963-7
        }
}
We investigate the thermally induced cyclization of 1,2-bis(2-phenylethynyl)benzene on Au(111) using scanning tunneling microscopy and computer simulations. Cyclization of sterically hindered enediynes is known to proceed via two competing mechanisms in solution: a classic C(1)-C(6) (Bergman) or a C(1)-C(5) cyclization pathway. On Au(111), we find that the C(1)-C(5) cyclization is suppressed and that the C(1)-C(6) cyclization yields a highly strained bicyclic olefin whose surface chemistry was… Expand
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References

SHOWING 1-10 OF 32 REFERENCES
Thermal C1-C5 diradical cyclization of enediynes.
TLDR
Thermolyses in the absence of 1,4-CHD as well as deuterium labeling studies confirm the existence of direct C1-C5 diradical cyclizations for diaryl-substituted enediynes. Expand
SYNTHESIS OF POLYPHENYLENES AND POLYNAPHTHALENES BY THERMOLYSIS OF ENEDIYNES AND DIALKYNYLBENZENES
Abstract : Described are the syntheses of substituted enediynes and dialkynylbenzenes using Pd- or Pd/Cu-catalyzed cross coupling procedures. The products were then thermalized, generally in benzene,Expand
Synthesis of polyphenylene derivatives by thermolysis of enediynes and dialkynylaromatic monomers
Abstract Described are the syntheses of substituted enediynes and dialkynylaromatics using Pd- or Pd Cu -catalyzed cross coupling procedures. The products were then thermalized to afford theExpand
Bergman cyclization of sterically hindered substrates and observation of phenyl-shifted products.
TLDR
The computed barriers for phenyl shifting are dramatically higher than those observed in the case of sp3 radicals, and these transformations are relevant in solution chemistry as well as in more extreme environments such as those encountered during combustion, pyrolysis, and electric discharge heating. Expand
Enediyne dimerization vs Bergman cyclization.
High-level quantum chemical calculations reveal that the dimerization of enediynes to 1,3-butadiene-1,4-diyl diradicals is energetically more favored than the corresponding Bergman cyclization ofExpand
Can Fulvenes Form from Enediynes? A Systematic High-Level Computational Study on Parent and Benzannelated Enediyne and Enyne−Allene Cyclizations
Apart from the well-known Bergman, Myers−Saito, and Schmittel ring closure reactions of parent enediyne (4) and enyne−allene (3), novel cyclization modes were identified using density functionalExpand
Reversible Bergman cyclization by atomic manipulation.
TLDR
A reversible, triggered Bergman cyclization is demonstrated for the first time and switching on demand between the two reactive intermediates by means of selective C-C bond formation or cleavage is demonstrated, which opens up the field of radical chemistry for on-surface reactions by atomic manipulation. Expand
Concerted reactions that produce diradicals and zwitterions: electronic, steric, conformational, and kinetic control of cycloaromatization processes.
TLDR
The data suggested that products from both polar and free radical reaction pathways arise either from a single reactive intermediate or from a pair of rapidly equilibrating species, which suggests that the partitioning between the diradical and zwitterionic pathways occurs after the rate-determining TS. Expand
Local Electronic and Chemical Structure of Oligo-acetylene Derivatives Formed Through Radical Cyclizations at a Surface
TLDR
The combined structural and electronic measurements reveal that the energy associated with extended π-conjugated states in these oligomers is significantly lower than the energy of the corresponding localized monomer orbitals, consistent with theoretical predictions. Expand
On-surface formation of one-dimensional polyphenylene through Bergman cyclization.
TLDR
On-surface formation of one-dimensional polyphenylene chains through Bergman cyclization followed by radical polymerization on Cu(110) using scanning tunneling microscopy imaging and density functional theory calculations is reported for the first time. Expand
...
1
2
3
4
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