Ruthenium promoter

Negishi E, Tan Z (2005) Diastereoselective, Enantioselective, and Regioselective Carbo-alumination Reactions Catalyzed by Zirconocene Derivatives. 8 139-176 Netherton M, Fu GC (2005)Pa]ladium-catalyzed Cross-Coupling Reactions of Unactivated Alkyl Electrophiles with Organometallic Compounds. 14 85-108 Nicolaou KC, King NP, He Y (1998) Ring-Closing Metathesis in the Synthesis of EpothUones and Polyether Natmal Products. 1 73-104 Nishiyama H (2004) Cyclopropanation with Ruthenium Catalysts. 11 81-92 Noels A, Demonceau A, Delaude L (2004) Ruthenium Promoted Catalysed Radical Processes toward Fine Chemistry. 11 155-171... 

Scheme 9.4 CATIVA - possible role of ruthenium promoter...

Li, J.L., Jacobs, G., Das, T.K., and Davis, B.H. 2002. Fischer-Tropsch synthesis Effect of water on the catalytic properties of a ruthenium promoted Co/Ti02 catalyst. Appl. Catal. 233 255-62. 

Tavasoli, A., Malek Abbaslou, R. M., and Dalai, A. K. 2008. Deactivation behavior of ruthenium promoted Co/a-Al203 catalysts in Fischer-Tropsch synthesis. Appl. Catal. A 346 58-64. 

Kogelbauer, A., Goodwin, Jr., J.G., and Oukaci, R. 1996. Ruthenium promotion of Co/A1203 Fischer-Tropsch catalysts. J. Catal. 160 125-33. 

In situ HPIR spectroscopy showed that the dominant Ir species under catalytic conditions are [IHCOUbMc]- and [Ir(CO)2l4] , both in the absence or presence of a promoter. A ruthenium promoter exists mainly as [Ru(CO)3l3], in equilibrium with smaller amounts of [Ru(CO)3l2(sol)] and [Ru(CO)2I2(sol)2]. 

Ruthenium-promoted oxidation of carbohydrates with sodium periodate... 

Selected examples of the ruthenium promoted reduction of nitroarenes... 

Noels A, Demonceau A, Delaude L (2004) Ruthenium Promoted Catalysed Radical Processes toward Fine Chemistry. 11 155-171 Nolan SP, see Dfez-Gonzalez S (2006) 21 47-82... 

With a ruthenium promoter (added as [Ru(CO)4l2]), r(CO) bands due to Ru iodo-carbonyls dominated the spectrum, precluding the easy observation of iridium species. Before injection of the Ir catalyst, absorptions due to [Ru(CO)2l2(sol)2], [Ru(CO)3l2(sol)] and [Ru(CO)3l3] are present. After injection of the iridium catalyst (Ru Ir = 2 1), [Ru(CO)3l3] becomes the dominant Ru species (Figure 3.11(b)). The observations indicate that the Ru(II) promoter has a high affinity for iodide and scavenges Hl(aq) as H30 [Ru(CO)3l3] . An indium promoter is believed to behave in a similar manner to form H30 [Inl4] . These promoter species also catalyse the reaction of Hlj q) with methyl acetate (Eq. (3)), which is an important organic step in the overall process. 

The bis(phosphetanyl)benzenes 80 and bis(phosphetanyl)ethane 71 also show a significant potential in ruthenium-promoted hydrogenations of functionalized carbonyl derivatives (Equation 19) <1999CEJ1160, 2000T95, 2001JOM(624)162>. With ligands 80, the catalytic activity is moderate, so rather severe reaction conditions must be employed (80 bar, 80 °C). 

A ruthenium-promoted carbonylation of allenyl alcohols 884 is a powerful method for the synthesis of 5,6-dihydropyran-2-ones 885 (Equation 356) <20000L441, 2003JOC8571>. Co2(CO)6-mediated tandem [5+1]/ [2+2+1] cycloaddition reactions of the epoxide 886 with carbon monoxide provide a one-pot synthesis of tricyclic 5,6-dihydropyran-2-ones 887 in good yield (Equation 357) <2003JA9610>. 

Nagashima H (2004) Ruthenium-promoted radical reactions. In Murahashi S-i (ed) Ruthenium in organic synthesis. Wiley-VCH, Weinheim, p 333... 

Reactions involving radical reactions are detailed in the chapter Ruthenium-Promoted Radical Processes Toward Fine Chemistry of this volume. 

Ruthenium-Promoted Radical Processes Toward Fine Chemistry... 

Ruthenium-promoted formation of 1/7-phosphindoles from phosphaalkynes <2007JA14962>. 

Interest in iridium-catalyzed methanol carbonylation was rekindled in the 1990 s when BP Chemicals developed and commercialized the Cativa process, which utilizes an iridium/iodide catalyst and a ruthenium promoter. This process has the important advantage that the highest catalytic rates occur at significantly lower water concentration (ca. 5% wt) than for Monsanto s... 

A range of compounds enhance the activity of an iridium catalyst. The promoters fall into two categories (i) carbonyl or halocarbonyl complexes of W, Re, Ru, Os and Pt and (ii) simple iodides of Zn, Cd, Hg, Ga and In. The preferred ruthenium promoter is effective over a range of water concentrations the maximum rate being attained at ca. 5% wt H2O, as in the absence of promoter. By contrast, ionic iodides such as Lil and BU4NI are strong catalyst poisons. 

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