Ruthenium phosphorus containing

This study, performed on the hydroformylation of oct-l-ene, has shown that below 140°C nonanals are the predominant products with linearities of approximately 97% (99% in one run at I00°C), whereas above 180°C nonanol was obtained almost exclusively with high octene conversions (>98% at 200°C) but poor linearities (65%). At high temperatures a 10-fold excess of bipy increases the nonanol linearity (to 76%). This parameter is not very sensitive to the CO or partial pressures as the total pressure is above about 95 bar. The author (40) seems to prefer coordination of the alkenc to a ruthenium center or hydride transfer to form an alkyl ruthenium cluster as the two possible rate-determining steps. Thus, by optimization of the experimental conditions it is possible to reach high linearities (n/iso>100) for the hydroformylation of terminal alkenes by the [Ru3(CO),2]/bidentate nitrogen- or phosphorus-containing ligand/phos-... 

Caminade and Majoral reacted phosphorus-containing dendrimers with various transition metal complexes (Fig. 7) [ 113 ]. Via phosphane, diphosphane, or P=N-P=S ligands, they were able to incorporate several metals (Pd, Pt, Rh, Au, Fe, W, Zr) either in the core or in the periphery of their dendrimers. The dendritic palladium and ruthenium complexes 7 have been introduced in Stille couplings, Knoevenagel condensations and diastereoselective Michael additions. A positive dendritic effect and high stability of dendritic Pd complexes has been observed. Separation occurred by precipitation with ether and reuse was reported. 

We have prepared a variety of metalladendrimers from the reaction of phosphorus-containing dendrimers with various transition metal complexes. Dendritic complexes incorporating metals such as gold [28a, 57], iron [57,58,59], tungsten [58,59], rhodium [59, 60], platinum [60], palladium [61], ruthenium [62], or zirconium [63] were prepared. 

Enantioseiective Reduction (Section 6.7) The most useful chiral hydrogenation catalysts involve a chiral phosphorus-containing ligand complexed with either ruthenium or rhodium. 

As with previous publications (GOMG (1982) and GOMG (1995)), phosphorus ligands feature heavily in the chemistry of ruthenium and osmium. In many instances the focus of the publications is such that the phosphorus-containing species are peripheral to the specific reactivity that a publication might be dealing with. For this reason, phosphorus ligands are somewhat ubiquitous within cluster chemistry. Here, an attempt has been made to focus on the phosphorus and its interaction with the cluster. 

Ruthenium clusters containing oxygenated diphosphine ligands Triruthenium and triosmium clusters obtained through orthometallation reactions Triruthenium complexes isolated during catalytic experiments Addition of phosphorus ligands to cationic triosmium complexes Miscellaneous oomplexes... 

Ligands Bonded through Carbon and Phosphorus 6.22.3.2.1 Ruthenium clusters containing oxygenated diphosphine ligands... 

A ruthenium(II) complex (5,5,55)-BrXuPHOS-Ru-DPEN (4) containing BINOL-based monodonor phosphorus ligand BrXuPHOS (1) has been prepared and applied as a catalyst (S/C = up to 10000) for the asymmetric hydrogenation of ketones, providing the enantiomerically pure secondary alcohols with up to 99 % ee. 

A series of cationic, strapped, r)6 ri1 ri1-arene complexes of ruthenium(II) (82) containing both carbon and phosphorus as the auxiliary atoms has been obtained by a coupling reaction of the iminophosphorane complexes 83 with an excess of 1, l-diphenyl-2-propyn-l-ol, the p-cymene in 83 being displaced by one of the phenyl... 

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