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[Display omitted] Reactions of the electron defficient triosmium [Os 3 (CO) 9 (μ 3 -η1,κ1-C 9 H 6 N)(μ-H)] with Ph 3 EH (E = Si, Ge, Sn) have been investigated. The reactions of quinoline-capped triosmium cluster [Os 3 (CO) 9 (μ 3 -η1,κ1-C 9 H 6 N)(μ-H)] (1) with Ph 3 EH (E = Si, Ge, Sn) have been investigated. Cluster 1 reacts with Ph 3 EH in refluxing benzene to afford [Os 3 (CO) 9 (EPh 3)(μ-η1,κ1-C 9 H 6 N)(µ-H) 2 ] (2a , E = Si; 2b , E = Ge; 2c , E = Sn) and [Os 3 (CO) 8 (EPh 3)(μ 3 -η1,κ1-C 9 H 6 N)(µ-H) 2 ] (3a , E = Si; 3b , E = Ge; 3c , E = Sn). Control experiments confirm that 2 is a precursor of 3. Cluster 2 is formed via oxidative-addition of E–H bond to 1 whose decarbonylation leads to the formation of 3. The molecular structures of all the new clusters (except 3c) have been determined by X-ray crystallography. Both 2 and 3 exist as a pair of isomers in solution, and their fluxionality in solution has been probed by VT NMR experiments. [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel Rh-containing non-phosphorous supported catalysts for tandem hydroformylation-hydrogenation were obtained. • Tertiary nitrogen atoms of the polymer anchored on material's surface promote aldehyde hydrogenation over Rh active centers. • Catalysts showed high activity (hydroformylation TOF 206 h−1) and chemoselectivity. • Catalyst K N performed stable hydroformylation yield at least in the first 5 cycles with a decrease in alcohol selectivity. Non-phosphorous rhodium-containing catalysts for direct conversion of olefins to alcohols via tandem hydroformylation/hydrogenation have been designed and synthesized. Interaction between Rh(acac)(CO) 2 and tertiary amino groups on the surface of mesoporous hybrid organic-inorganic supports yielded materials which were successfully used in the tandem process. Data obtained for a selected catalyst K N demonstrate that rhodium is in the Rh+1 state highly dispersed on the surface and is bonded with nitrogen atoms both before and after use. Evaluation of the catalytic performance shows high activity (hydroformylation TOF 312 h−1), chemoselectivity and stable hydroformylation yield at least in the first 5 cycles with a decrease in alcohol selectivity. The influence of temperature, reaction time, total pressure, and molar CO/H 2 ratio of syngas on oxygenate yields is described. Type of the hydroformylation active sites and possible pathways for the observed decrease in hydrogenation are discussed. [ABSTRACT FROM AUTHOR]