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Abstract

The reactivity and bonding of allyl groups (C3H5) on a Ag(111) surface have been investigated under ultrahigh vacuum conditions by temperature-programmed reaction/desorption (TPR/D) and reflection-adsorption infrared spectroscopy (RAIRS). The atomically clean surface was achieved by Ar+ sputtering and verified by AES. The surface crystallinity was assured by LEED. Surface -bound allyl groups were generated by dissociative adsorption of allyl halides. Our study shows that the C-X (X= I or Cl) bond can be ruptured below 200K to render adsorbed allyl species. Upon further heating, three gas-phase products were detected at ~280 K, 295 K and 320 K in the TPR/D spectra, which are attributed to 1,5-hexadiene, allene, and propene, respectively. These results suggest that allyl undergoes

Table of Contents

Chapter 1 Introduction………………..……..……………..1

Chapter 2 Experimental Section
2.1 UHV System……….…………………………………...…....8
2.2 Preparation and Verification of a clean Substrate……….….13
2.3 Reagent Purification and Synthesis…………….…..….…….15
2.4 Experimental Procedure…………………….………………23

Chapter 3 Results
3.1 The Surface Chemistry of Propyl Iodide on Ag(111).………25
3.2 The Surface Chemistry of Allyl Iodide on Ag(111)……..….30
3.3 The Surface Chemistry of Allyl Chloride on Ag(111)…..….37
3.4 The Coupling Product: 1,5- or 2,4-Hexadiene……………….40
3.5 Coadsorption of Allyl Iodide and Propyl Iodide………..…..43
3.6 Coadsorption of Trifluoromethyl Iodide and Allyl Iodide…..46
3.7 The Surface Chemistry of Allyl-d1 Iodide on Ag(111)……...50
3.8 The Surface Chemistry of 1-chloro-1-propene on Ag(111)....53
3.9 RAIRS Spectra of Allyl Iodide on Ag(111)……….………..56

Chapter 4 Discussion
4.1 Mechanism of Surface Reactions……………….……….…63
4.2 β-Hydride Elimination…………………………….……...68
4.3 Isotopic Effect……………………………………….……..72

Chapter 5 Conclusion……………………………..…..79
References………………………………………….…………..83

Appendix……………………………………………………….89

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