Foundation of Surface Organometallic Chemistry

In parallel the proposal that the surface of a metal oxide behaves as a ligand of a surface organometaiiic molecular species arose from different observations, made particularly by Basset and Ugo in the late 1970s-early 1980s  

During the chemisorptions of Ru3(CO)i2 or Os3(CO)i2 on silica, the first step with the surface silanols was to produce a covalent bonding with the silica surface by oxidative addition of the silanol group to the metal-metal bond of the clusters. The nature of surface molecular species [=Si-0)(M3( x-H)(CO)io)j covalently linked to the silica surface (M = Ru, Os) was clearly defined and structurally characterized by a series of physical and chemical techniques, including mass balance taking into account the evolution of two molecules of CO and one molecule of hydrogen [27, 33, 35]. 

Simultaneously, it was shown that the OH groups of basic surfaces such as magnesia or alumina could behave as nucleophiles toward CO coordinated to 

However, when Ru3(CO)i2 was adsorbed on the surface of a basic metal oxide such as the decarbonated surface of magnesia, a similar nucleophilic attack was demonstrated to occur with formation of the anionic [HRusjCOjn] species on the magnesia surface [42]. 

Structural evidences of the nature of surface organometallic species were confirmed in a few cases by the synthesis and structural characterization of molecular models (in particular using silanolate ligands) of surface organometallic 

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