An investigation of the surface chemistry of methyl pyruvate on Cu(111)

C. Fleming, J. Johnston, M. Kadodwala

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The surface chemistry of an alpha-ketoester, methyl pyruvate, has been studied on a model Cu(111) single crystal surface. Monolayers of methyl pyruvate at 180 K consist predominately (ca. 66%) of a chemisorbed methyl pyruvate moiety, with its keto-carbonyl bonded to the surface in a eta(2) configuration, this moiety desorbs intact at 365 K. The rest of the monolayer contains weakly adsorbed methyl pyruvate, which desorbs at 234 K, which interacts with the surface through the lone pair electrons of the oxygen atoms of the C=O groups, adopting a 711 configuration. Previous studies of simple ketones on model noble metal surfaces have only observed weakly bonded eta(1) configurations. The observation of a strongly chemisorbed moiety in the present study is attributed to the activation of the keto-carbonyl by the electron withdrawing ester group. This behaviour is consistent with the homogeneous inorganic chemistry of ketones. Given both the formation of a eta(2) bonded methyl pyruvate moiety on Cu(l 11) and the known activity of Cu as a selective hydrogenation catalyst, it is suggested that it maybe worthwhile considering the possibility of testing the effectiveness of chirally modified supported Cu as an enantioselective catalyst.
LanguageEnglish
Pages5485-5491
Number of pages7
JournalSurface Science
Volume601
Issue number23
DOIs
Publication statusPublished - 1 Dec 2007

Fingerprint

pyruvates
Surface chemistry
chemistry
Ketones
Monolayers
Single crystal surfaces
Catalysts
Electrons
ketones
Precious metals
configurations
Hydrogenation
inorganic chemistry
Esters
catalysts
Chemical activation
Atoms
noble metals
Oxygen
crystal surfaces

Keywords

  • surfaces
  • chirality
  • enantioselective heterogeneous catalysis
  • a-ketoesters
  • methyl pyruvate
  • asymmetric catalysis

Cite this

Fleming, C. ; Johnston, J. ; Kadodwala, M. / An investigation of the surface chemistry of methyl pyruvate on Cu(111). In: Surface Science. 2007 ; Vol. 601, No. 23. pp. 5485-5491 .
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An investigation of the surface chemistry of methyl pyruvate on Cu(111). / Fleming, C.; Johnston, J.; Kadodwala, M.

In: Surface Science, Vol. 601, No. 23, 01.12.2007, p. 5485-5491 .

Research output: Contribution to journalArticle

TY - JOUR

T1 - An investigation of the surface chemistry of methyl pyruvate on Cu(111)

AU - Fleming, C.

AU - Johnston, J.

AU - Kadodwala, M.

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N2 - The surface chemistry of an alpha-ketoester, methyl pyruvate, has been studied on a model Cu(111) single crystal surface. Monolayers of methyl pyruvate at 180 K consist predominately (ca. 66%) of a chemisorbed methyl pyruvate moiety, with its keto-carbonyl bonded to the surface in a eta(2) configuration, this moiety desorbs intact at 365 K. The rest of the monolayer contains weakly adsorbed methyl pyruvate, which desorbs at 234 K, which interacts with the surface through the lone pair electrons of the oxygen atoms of the C=O groups, adopting a 711 configuration. Previous studies of simple ketones on model noble metal surfaces have only observed weakly bonded eta(1) configurations. The observation of a strongly chemisorbed moiety in the present study is attributed to the activation of the keto-carbonyl by the electron withdrawing ester group. This behaviour is consistent with the homogeneous inorganic chemistry of ketones. Given both the formation of a eta(2) bonded methyl pyruvate moiety on Cu(l 11) and the known activity of Cu as a selective hydrogenation catalyst, it is suggested that it maybe worthwhile considering the possibility of testing the effectiveness of chirally modified supported Cu as an enantioselective catalyst.

AB - The surface chemistry of an alpha-ketoester, methyl pyruvate, has been studied on a model Cu(111) single crystal surface. Monolayers of methyl pyruvate at 180 K consist predominately (ca. 66%) of a chemisorbed methyl pyruvate moiety, with its keto-carbonyl bonded to the surface in a eta(2) configuration, this moiety desorbs intact at 365 K. The rest of the monolayer contains weakly adsorbed methyl pyruvate, which desorbs at 234 K, which interacts with the surface through the lone pair electrons of the oxygen atoms of the C=O groups, adopting a 711 configuration. Previous studies of simple ketones on model noble metal surfaces have only observed weakly bonded eta(1) configurations. The observation of a strongly chemisorbed moiety in the present study is attributed to the activation of the keto-carbonyl by the electron withdrawing ester group. This behaviour is consistent with the homogeneous inorganic chemistry of ketones. Given both the formation of a eta(2) bonded methyl pyruvate moiety on Cu(l 11) and the known activity of Cu as a selective hydrogenation catalyst, it is suggested that it maybe worthwhile considering the possibility of testing the effectiveness of chirally modified supported Cu as an enantioselective catalyst.

KW - surfaces

KW - chirality

KW - enantioselective heterogeneous catalysis

KW - a-ketoesters

KW - methyl pyruvate

KW - asymmetric catalysis

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