Description:
<jats:title>Abstract</jats:title><jats:p>1,1′‐Difunctionalised ferrocene derivatives have been studied, which contain groups suitable for chemisorption on gold substrates, namely NC, PR<jats:sub>2</jats:sub> as well as a range of sulfur‐containing units like NCS, SR, and thienyl. Thin films on gold have been fabricated from solution with most of these adsorbate species. Film thickness, composition and structure were investigated primarily by X‐ray photoelectron and near‐edge X‐ray absorption fine‐structure spectroscopy. The quality of self‐assembled monolayers fabricated from 1,1′‐diisocyanoferrocene (<jats:bold>1</jats:bold>) and 1,1′‐diisothiocyanatoferrocene (<jats:bold>2</jats:bold>) turned out to be superior to that of films based on the other adsorbate species investigated. In addition to the surface coordination behaviour of <jats:bold>1</jats:bold> towards gold substrates, relevant aspects of the molecular coordination chemistry of <jats:bold>1</jats:bold> have also been addressed, including the synthesis and characterisation of [(μ‐<jats:bold>1</jats:bold>){Cr(CO)<jats:sub>5</jats:sub>}<jats:sub>2</jats:sub>], [Ag<jats:sub>2</jats:sub>(μ‐<jats:bold>1</jats:bold>)<jats:sub>2</jats:sub>](NO<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub><jats:bold>⋅</jats:bold>H<jats:sub>2</jats:sub>O and [(μ‐<jats:bold>1</jats:bold>)(AuCl)<jats:sub>2</jats:sub>]. The crystal structure of the gold complex is governed by aurophilic interactions and can be taken as a model for the arrangement of <jats:bold>1</jats:bold> in self‐assembled monolayers on gold.</jats:p>