The continuous decrease in size of electronic devices has reached a critical point at which the molecular-level understanding of chemical processes is imperative. Metal-containing films, an important part of every circuit, are currently deposited from a myriad of organometallic compounds, in order to control the first stages of film growth and ultimately produce an atomically defined interface. This article outlines recent molecular-level investigations on reactions of organometallic compounds with silicon surfaces. The role of surface structure and chemical state is placed in a framework of future challenges and opportunities for applications in electronics.