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Heck Coupling of Olefins to Mixed Methyl/Thienyl Monolayers on Si(111) Surfaces

O’Leary, Leslie E. and Rose, Michael J. and Ding, Tina X. and Johansson, Erik and Brunschwig, Bruce S. and Lewis, Nathan S. (2013) Heck Coupling of Olefins to Mixed Methyl/Thienyl Monolayers on Si(111) Surfaces. Journal of the American Chemical Society, 135 (27). pp. 10081-10090. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20130829-095118486

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Abstract

The Heck reaction has been used to couple olefins to a Si(111) surface that was functionalized with a mixed monolayer comprised of methyl and thienyl groups. The coupling method maintained a conjugated linkage between the surface and the olefinic surface functionality, to allow for facile charge transfer from the silicon surface. While a Si(111) surface terminated only with thienyl groups displayed a surface recombination velocity, S, of 670 ± 190 cm s^(–1), the mixed CH_3/SC_4H_3–Si(111) surfaces with a coverage of θ_(SC_4H_3) = 0.15 ± 0.02 displayed a substantially lower value of S = 27 ± 9 cm s^(–1). Accordingly, CH_3/SC_4H_3–Si(111) surfaces were brominated with N-bromosuccinimide, to produce mixed CH_3/SC_4H_2Br–Si(111) surfaces with coverages of θ_(Br–Si) < 0.05. The resulting aryl halide surfaces were activated using [Pd(PPh_3)_4] as a catalyst. After activation, Pd(II) was selectively coordinated by oxidative addition to the surface-bound aryl halide. The olefinic substrates 4-fluorostyrene, vinylferrocene, and protoporphyrin IX dimethyl ester were then coupled (in dimethylformamide at 100 °C) to the Pd-containing functionalized Si surfaces. The porphyrin-modified surface was then metalated with Co, Cu, or Zn. The vinylferrocene-modified Si(111) surface showed a linear dependence of the peak current on scan rate in cyclic voltammetry, indicating that facile electron transfer had been maintained and providing evidence of a robust linkage between the Si surface and the tethered ferrocene. The final Heck-coupled surface exhibited S = 70 cm s^(–1), indicating that high-quality surfaces could be produced by this multistep synthetic approach for tethering small molecules to silicon photoelectrodes.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja402495e DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja402495ePublisherArticle
ORCID:
AuthorORCID
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2013 American Chemical Society. Received: March 10, 2013; Published: June 26, 2013. This work was supported by the National Science Foundation (CHE-1214152) and the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology. The Link Foundation Energy fellowship (L.E.O.), the NSF ACC-F (M.J.R., CHE-1042009), and the John and Maria Laffin Trust SURF (T.X.D.) are gratefully acknowledged for graduate, postdoctoral, and undergraduate fellowship support. We acknowledge Dr. Ronald Grimm and Ms. Judith Lattimer for insightful discussions.
Funders:
Funding AgencyGrant Number
NSFCHE-1214152
Caltech Beckman InstituteUNSPECIFIED
Link FoundationUNSPECIFIED
NSFCHE-1042009
John and Maria Laffin TrustUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Issue or Number:27
Record Number:CaltechAUTHORS:20130829-095118486
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130829-095118486
Official Citation:Heck Coupling of Olefins to Mixed Methyl/Thienyl Monolayers on Si(111) Surfaces Leslie E. O’Leary, Michael J. Rose, Tina X. Ding, Erik Johansson, Bruce S. Brunschwig, and Nathan S. Lewis Journal of the American Chemical Society 2013 135 (27), 10081-10090
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40989
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Aug 2013 23:22
Last Modified:03 Oct 2019 05:44

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