Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by C andNa solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Au are observed. Na NMR experiments show that Na ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

The silica‐supported azazirconacyclopropane SiOZr(HNMe2)(η2‐NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150 °C) to the single‐site monopodal monohydride silica‐supported zirconium species SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by contacting compound 2 with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200 °C revealed alkene hydrogenation.

Grafting of Zr(NMe2)4 on mesoporous silica SBA-15 afforded selectively well-defined surface species [triple bond, length as m-dash]SiOZr(NMe2)(η2NMeCH2). 2D solid-state NMR ((1)H-(13)C HETCOR, Multiple Quantum) experiments have shown a unique structural rearrangement occurring on the immobilised zirconium bis methylamido ligand.

Intermolecular catalytic hydroaminoalkylation of unactivated alkene occurs with silica-supported azazirconacyclopropane [ Si À O À Zr(HNMe 2 )(h 2

Mechanistic study of hydroamination of alkyne through tantalum-based silicasupported surface species. ACS Catalysis.

The single-site silica-supported group IV metal amido complex [Ti(NMe 2 ) 4 ] gives the tris(amido)-supported fragment [(Si−O−)Ti(−NMe 2 ) 3 ], which transforms into a three-membered metallacycle (called a metallaaziridine) by an α-H transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M−C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three-and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins. Article pubs.acs.org/Organometallics

Monohydride silica‐supported zirconium The silica‐supported azazirconacyclopropane SiOZr(HNMe2)(η2‐NMeCH2)(NMe2) (1) leads exclusively under hydrogenolysis conditions (H2, 150 °C) to the single‐site monopodal monohydride silica‐supported zirconium species SiOZr(HNMe2)(NMe2)2H (2). Reactivity studies by allowing compound 2 to come into contact with ethylene, hydrogen/ethylene, propene, or hydrogen/propene, at a temperature of 200 °C revealed alkene hydrogenation. For more details, see the Full Paper by Jean‐Marie Basset et al. on

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