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Hydride Complexes of Ruthenium, Rhodium, and Iridium

Hydride Complexes of Ruthenium, Rhodium, and Iridium G. L. Geoffroy and J. R. Lehman Structures and Physical Properties of Polynuclear Carboxylates Janet Catterick and Peter Thornton... [Pg.440]

In the past, this field has been dominated by ruthenium, rhodium and iridium catalysts with extraordinary activities and furthermore superior enantioselectivities however, some investigations were carried out with iron catalysts. Early efforts were reported on the successful use of hydridocarbonyliron complexes HFcm(CO) as reducing reagent for a, P-unsaturated carbonyl compounds, dienes and C=N double bonds, albeit complexes were used in stoichiometric amounts [7]. The first catalytic approach was presented by Marko et al. on the reduction of acetone in the presence of Fe3(CO)12 or Fe(CO)5 [8]. In this reaction, the hydrogen is delivered by water under more drastic reaction conditions (100 bar, 100 °C). Addition of NEt3 as co-catalyst was necessary to obtain reasonable yields. The authors assumed a reaction of Fe(CO)5 with hydroxide ions to yield H Fe(CO)4 with liberation of carbon dioxide since basic conditions are present and exclude the formation of molecular hydrogen via the water gas shift reaction. H Fe(CO)4 is believed to be the active catalyst, which transfers the hydride to the acceptor. The catalyst presented displayed activity in the reduction of several ketones and aldehydes (Scheme 4.1) [9]. [Pg.126]

COMPLEXES OF RUTHENIUM, OSMIUM, RHODIUM, AND IRIDIUM CONTAINING HYDRIDE CARBONYL, OR NITROSYL LIGANDS... [Pg.45]

The intramolecular insertion of a hydride into a coordinated olefin is a crucial step in olefin hydrogenation catalyzed by late transition metal complexes, such as those of iridium, rhodium, and ruthenium (Chapter 15), in hydroformylation reactions catalyzed by cobalt, rhodium, and platinum complexes (Chapter 16), and in many other reactions, including the initiation of some olefin polymerizations. The microscopic reverse, 3-hydride elimination, is the most common pathway for the decomposition of metal-alkyl complexes and is a mechanism for olefin isomerizations. [Pg.366]

More recently, systems based on polypyridine coordination compounds of ruthenium(II) [46-49], rhodium(I) [50a] and iridium(I) [50] have been shown to efficiently catalyse the thermal WGSR. An important effect of the substituent ortho to the nitrogen atom of the ligand has been demonstrated in the case of Ir(I) leading to one of the most efficient catalysts known today [50b]. [Ru(bpy)2(CO)Cl] has also been studied and all of the possible intermediates within the catalytic cycle (hydrocarbonyl complex, metal hydride, aquo species) have been isolated and characterized [48]. [Pg.220]

One of the standard methods for preparing enantiomerically pure compounds is the enantioselective hydrogenation of olefins, a,/3-unsaturated amino acids (esters, amides), a,/3-unsaturated carboxylic acid esters, enol esters, enamides, /3- and y-keto esters etc. catalyzed by chiral cationic rhodium, ruthenium and iridium complexes ". In isotope chemistry, it has only been exploited for the synthesis of e.p. natural and nonnatural H-, C-, C-, and F-labeled a-amino acids and small peptides from TV-protected a-(acylamino)acrylates or cinnamates and unsaturated peptides, respectively (Figure 11.9). This methodology has seen only hmited use, perhaps because of perceived radiation safety issues with the use of hydrogenation procedures on radioactive substrates. Also, versatile alternatives are available, including enantioselective metal hydride/tritide reductions, chiral auxiliary-controlled and biochemical procedures (see this chapter. Sections 11.2.2 and 11.3 and Chapter 12). [Pg.530]


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Rhodium ruthenium

Ruthenium hydride

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Ruthenium, Rhodium, and Iridium

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