Noncovalent Dimerization after Enediyne Cyclization on Au(111)

Dimas G. De Oteyza; Alejandro Pérez Paz; Yen Chia Chen; Zahra Pedramrazi; Alexander Riss; Sebastian Wickenburg; Hsin Zon Tsai; Felix R. Fischer; Michael F. Crommie; Angel Rubio

doi:10.1021/jacs.6b05203

Noncovalent Dimerization after Enediyne Cyclization on Au(111)

Dimas G. De Oteyza, Alejandro Pérez Paz, Yen Chia Chen, Zahra Pedramrazi, Alexander Riss, Sebastian Wickenburg, Hsin Zon Tsai, Felix R. Fischer, Michael F. Crommie, Angel Rubio

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

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 C¹-C⁶ (Bergman) or a C¹-C⁵ cyclization pathway. On Au(111), we find that the C¹-C⁵ cyclization is suppressed and that the C¹-C⁶ cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C¹-C⁶ product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.

Original language	English
Pages (from-to)	10963-10967
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	138
Issue number	34
DOIs	https://doi.org/10.1021/jacs.6b05203
Publication status	Published - Aug 31 2016
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.6b05203

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@article{8466dd10857047b08dc51c647e7df6ef,

title = "Noncovalent Dimerization after Enediyne Cyclization on Au(111)",

abstract = "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 C1-C6 (Bergman) or a C1-C5 cyclization pathway. On Au(111), we find that the C1-C5 cyclization is suppressed and that the C1-C6 cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C1-C6 product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.",

author = "{De Oteyza}, {Dimas G.} and {P{\'e}rez Paz}, Alejandro and Chen, {Yen Chia} and Zahra Pedramrazi and Alexander Riss and Sebastian Wickenburg and Tsai, {Hsin Zon} and Fischer, {Felix R.} and Crommie, {Michael F.} and Angel Rubio",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = aug,

day = "31",

doi = "10.1021/jacs.6b05203",

language = "English",

volume = "138",

pages = "10963--10967",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "34",

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TY - JOUR

T1 - Noncovalent Dimerization after Enediyne Cyclization on Au(111)

AU - De Oteyza, Dimas G.

AU - Pérez Paz, Alejandro

AU - Chen, Yen Chia

AU - Pedramrazi, Zahra

AU - Riss, Alexander

AU - Wickenburg, Sebastian

AU - Tsai, Hsin Zon

AU - Fischer, Felix R.

AU - Crommie, Michael F.

AU - Rubio, Angel

PY - 2016/8/31

Y1 - 2016/8/31

N2 - 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 C1-C6 (Bergman) or a C1-C5 cyclization pathway. On Au(111), we find that the C1-C5 cyclization is suppressed and that the C1-C6 cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C1-C6 product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.

AB - 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 C1-C6 (Bergman) or a C1-C5 cyclization pathway. On Au(111), we find that the C1-C5 cyclization is suppressed and that the C1-C6 cyclization yields a highly strained bicyclic olefin whose surface chemistry was hitherto unknown. The C1-C6 product self-assembles into discrete noncovalently bound dimers on the surface. The reaction mechanism and driving forces behind noncovalent association are discussed in light of density functional theory calculations.

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U2 - 10.1021/jacs.6b05203

DO - 10.1021/jacs.6b05203

M3 - Article

AN - SCOPUS:84984801049

SN - 0002-7863

VL - 138

SP - 10963

EP - 10967

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

Noncovalent Dimerization after Enediyne Cyclization on Au(111)

Abstract

ASJC Scopus subject areas

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