Supported Cobalt Nanoparticles for Hydroformylation Reactions.

Hydroformylation of olefins has been studied in the presence of specific heterogeneous cobalt nanoparticles. The catalytic materials were prepared by pyrolysis of preformed cobalt complexes deposited onto different inorganic supports. Atomic absorption spectroscopy (AAS) measurements indicated a correlation of catalyst activity and cobalt leaching as well as a strong influence of the heterogeneous support on the productivity. These new, low-cost, easy-to-handle catalysts can substitute more toxic, unstable and volatile cobalt carbonyl complexes for hydroformylations on a laboratory scale.

Hydrogenation of terminal and internal olefins using a biowaste-derived heterogeneous cobalt catalyst.

Hydrogenation of olefins is achieved using biowaste-derived cobalt chitosan catalysts. Characterization of the optimal Co@Chitosan-700 by STEM (scanning transmission electron microscopy), EELS (electron energy loss spectroscopy), PXRD (powder x-ray diffraction), and elemental analysis revealed the formation of a distinctive magnetic composite material with high metallic Co content. The general performance of this catalyst is demonstrated in the hydrogenation of 50 olefins including terminal, internal, and functionalized derivatives, as well as renewables. Using this nonnoble metal composite, hydrogenation of terminal C==C double bonds occurs under very mild and benign conditions (water or methanol, 40° to 60°C). The utility of Co@Chitosan-700 is showcased for efficient hydrogenation of the industrially relevant examples diisobutene, fatty acids, and their triglycerides. Because of the magnetic behavior of this material and water as solvent, product separation and recycling of the catalyst are straightforward.

Azidophosphenium cations: versatile reagents in inorganic synthesis.

This work describes the synthesis and characterization of a series of iminophosphorane-substituted phosphenium cations of the type [R2NPNP(Cl)2NPNR'2][GaCl4] [R = iPr; R' = iPr (7[GaCl4]), SiMe3 (8)], which are directly derived from azidophosphenium salt [iPrNPN3][GaCl4] (2iPr[GaCl4]) and the corresponding chlorophosphane R2NPCl2. The reactivity of 7[GaCl4] toward 2,3-dimethylbutadiene (dmb) and 2,2'-bipyridine (bipy) was investigated, resulting in the formation of 7-dmb[GaCl4] and 7-Cl. In addition, self-condensation of [(Me3Si)2NPN3][GaCl4] (2SiMe3[GaCl4]) was studied in detail, and [(Me3Si)2NPNP(XY)N(SiMe3)2][GaCl4] [X = Cl; Y = Cl (13), N3 (14)] were determined as products on the basis of (31)P NMR spectroscopy. The reaction of 2SiMe3[GaCl4] with [(Me3Si)2NPCl][GaCl4] (1SiMe3[GaCl4]) yielded an unprecedented bicyclic 1,3,2λ(3),4λ(5)-diazadiphosphetidine (15), which was formed via a GaCl3-assisted Me3SiCl elimination starting from 13. Furthermore, cations of the type [R2NPNPR'3][GaCl4] [R = iPr; R' = cHex (19)] were obtained by the effective combination of 2R[GaCl4] (R = iPr, SiMe3) with PR'3 (R' = Ph, cHex). Azidochlorophosphanes R2NP(N3)Cl [R = iPr, SiMe3 (20R)] are shown to be accessible when 2R[GaCl4] was combined with bipy. All new compounds were fully characterized by means of X-ray, vibrational spectroscopy, CHN analysis, and NMR experiments. All compounds were further investigated by means of density functional theory, and the bonding situation was accessed by natural bond orbital analysis.