On the Origins and Development of “Surface Organometallic Chemistry”

Well-defined silica supported aluminum hydride: another step towards the utopian single site dream?

“…66 However, as previously describes by Espinas et al 27 Al NMR signals are notoriously difficult to observe to very broad line shape. 41 As frequently observed in SOMC, 2 Al center coordinate to the silica surface (Si–O–Si) affording Al-surfaces complexes with different Al chemical shifts. The Al Oh species are closer to the surface and so are assumed to be due to the reaction of TIBA with the strained siloxane whereas the Al Th species are issued from the reaction of single silanol with TIBA.…”

“…9–14 One of the simplest ways to make such models compounds is to react the surface silanols (Si–OH) of partially dehydroxylated silica with a metal-alkyl to obtain in principle well defined grafted complexes. 2,9,15,16 However, it appeared progressively that depending on the degree of dehydroxylation of a support, mono, bi and multipodal species can be generated. 2,9,17–19 …”

“…2,9,15,16 However, it appeared progressively that depending on the degree of dehydroxylation of a support, mono, bi and multipodal species can be generated. 2,9,17–19 …”

Exploiting Chemistry to Improve Performance of Screen-Printed, Bismuth Film Electrodes (SP-BiFE)

“…The Bi(NO 3 ) 3 precursor has been dissolved into the polymer solution prior its casting onto the graphite surface of the working electrode, in order to maximize their interaction. As it was observed with metal/oxide catalytic surfaces [ 28 , 29 ], oxophilic metal ions may tend to graft themselves to the oxygen ligands of the surface, with an optimal distribution on the surface, preventing the growth of large particles after casting. Then, the zerovalent bismuth film was obtained by performing eight blank cycles under the same experimental conditions used for the stripping analysis (see Experimental section).…”

Design and Use of Nanostructured Single-Site Heterogeneous Catalysts for the Selective Transformation of Fine Chemicals

“…Twenty-five years ago Basset and co-workers introduced the concept of surface organometallic chemistry [ 58 ], starting a work based on the systematic study of the reactivity of organometallic complexes or coordination compounds with the surface of support materials, in particular functionalizing the surface of a non-porous pyrogenic (Aerosil) silica [ 4 , 59 ], and developing the idea according to which a metal oxide behaves as a ligand for a surface organometallic molecular species [ 60 , 61 ]. Their work produced SSHC before the advent of ordered mesoporous silicas, by appropriately functionalizing the residual pendant silanol groups on Aerosil (whose typical surface area is 200 m 2 g -1 and silanol surface concentration 0.7 ± 0.2 per nm 2 , equivalent to 0.23 mol(OH) g -1 ).…”