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The study of the effects of metal overlayers on organic self-assembled monolayers (SAMs) is of interest in many scientific areas. The self-assembly process leads to a well-defined substrate whereas the numerous combinations of end-groups and metals allows for the fine-tuning of the chemistry at the monolayer/metal interface. These unique features make metal/SAM interfaces a valuable tool for probing fundamental processes. SAM/metal interfaces, have been proposed as templates to elucidate details on, for example, metal/"organic host" interactions which are known to occur in biologically active metallic reaction sites [1]; reaction mechanisms at organic/metal/gas interfaces, such as those involved in heterogeneous catalysis and environmental chemistry [2]; the solvation and electron-transfer reactions of metals in molecular solvents or within molecular clusters [3, 4]; and the insertion of zero-valent metals into chemical bonds frequently found in homogeneous catalysis reactions [3, 4, 5, 6]. [ABSTRACT FROM AUTHOR]