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dc.contributor.authorPecher, Lisa
dc.contributor.authorLaref, Slimane
dc.contributor.authorRaupach, Marc
dc.contributor.authorTonner, Ralf Ewald
dc.date.accessioned2017-09-20T06:02:14Z
dc.date.available2017-09-20T06:02:14Z
dc.date.issued2017-09-15
dc.identifier.citationPecher L, Laref S, Raupach M, Tonner RE (2017) Ethers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry. Angewandte Chemie International Edition. Available: http://dx.doi.org/10.1002/anie.201707428.
dc.identifier.issn1433-7851
dc.identifier.doi10.1002/anie.201707428
dc.identifier.doi10.1002/ange.201707428
dc.identifier.urihttp://hdl.handle.net/10754/625480
dc.description.abstractUsing computational chemistry, we show that the adsorption of ether molecules on Si(001) under ultra-high vacuum conditions can be understood with textbook organic chemistry. The two-step reaction mechanism of (1) dative bond formation between the ether oxygen and a Lewis acidic surface atom and (2) a nucleophilic attack of a nearby Lewis basic surface atom is analysed in detail and found to mirror the acid-catalysed ether cleavage in solution. The O-Si dative bond is found to be the strongest of its kind and reactivity from this state defies the Bell-Evans-Polanyi principle. Electron rearrangement during the C-O bond cleavage is visualized using a newly developed bonding analysis method, which shows that the mechanism of nucleophilic substitutions on semiconductor surfaces is identical to molecular chemistry SN2 reactions. Our findings thus illustrate how the fields of surface science and molecular chemistry can mutually benefit and unexpected insight can be gained.
dc.description.sponsorshipThis work was supported by the Deutsche Forschungsgemeinschaft(DFG) within SFB 1083, GRK 1782 and TO 715/1-1. Computational resources were provided by HRZ Marburg, HLR Stuttgart and CSC-LOEWE Frankfurt. We thank Prof. Ulrich Koert, Prof. Ulrich Höfer (Marburg), Prof. Michael Dürr (Gießen), and Prof. Stacey Bent (Stanford) for discussions.
dc.publisherWiley-Blackwell
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/anie.201707428/abstract
dc.rightsThis is the peer reviewed version of the following article: Ethers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry, which has been published in final form at http://doi.org/10.1002/anie.201707428. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.
dc.subjectbonding analysis
dc.subjectdensity functional theory
dc.subjectether cleavage
dc.subjectsurface chemistry
dc.subjecttransfer of concepts
dc.titleEthers on Si(001): A prime example for the common ground between surface science and molecular organic chemistry
dc.typeArticle
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalAngewandte Chemie International Edition
dc.eprint.versionPost-print
dc.contributor.institutionFaculty of Chemistry and Material Sciences Center, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032 Marburg, Germany
kaust.personLaref, Slimane


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