Ligand-catalyzed

A further dramatic comparison of the comparative reactivities of chromium alkyls in diverse oxidation states was furnished by another set of benzyl complexes. [7] Shown below, these three compound are isomers, yet they range in oxidation state from Cr to Cr °. Of the three, only the mixed-valent complex Cp G0i-ti n3-Bz)Cr(Bz)Cp, containing a Bivalent chromium bound to an T)3-benzyl and a ni-benzyl ligand, catalyzed the polymerization of ethylene. 

Dimethyltitanium complex 25, bearing an ethylene and methyl ligands, catalyzed the dimerization of ethylene via a metallacyclopentane intermediate 26 (Eq. 1) [30]. During the dimerization, no insertion of ethylene into the Ti-Me bond was observed due to the perpendicular orientation between methyl and ethylene ligands. This inertness could be attributed to the low oxidation state of 25, i.e. Ti(II). 

Enantioselective catalytic hydrogenation. The ruthenium(II) complexes of (R)- and (S)-l, bearing a chiral BINAP ligand, catalyze asymmetric hydrogenation of N-acyl-l-alkylidenetetrahydroisoquinolines to give (1R)- or (lS)-tetrahydroiso-quinolines in 95-100% ee.1 Thus the (Z)-enamide (2), prepared by acylation of 3,4-dihydropapaverine, is hydrogenated in the presence of (R)-l to (1R)-tetrahydroisoquinolines (3). The enantiomeric (lS)-3 is obtained on use of (S)-l as catalyst. 

In situ-generated iridium complexes containing bulky 3,3 -substituted H8-phosphoroamidites 20 as ligands catalyzed the asymmetric hydrogenation of... 

Catalysts lacking phosphorus ligands have also been used as catalysts for allylic substitutions. [lr(COD)Cl]2 itself, which contains a 7i-accepting diolefin ligand, catalyzes the alkylation of allylic acetates, but the formation of branched products was only favored when the substitution reaction was performed with branched allylic esters. Takemoto and coworkers later reported the etherification of branched allylic acetates and carbonates with oximes catalyzed by [lr(COD)Cl]2 without added ligand [47]. Finally, as discussed in Sect. 6, Carreira reported kinetic resolutions of branched allylic carbonates from reactions of phenol catalyzed by the combination of [lr(COE)2Cl]2 and a chiral diene ligand [48]. 

In contrast, 1,5-cyclo-octadiene remains coordinated during the catalytic cycle of hydrogenation of phenylacetylene to styrene, catalyzed by the related iridium complex [Ir(C0D)( Pr2PCH2CH20Me)]BF4. This complex, which contains an ether-phosphine-chelated ligand, catalyzes the selective hydrogenation reaction via a dihydrido-cyclo-octadiene intermediate. The reaction is first order in each of catalyst, phenylacetylene and hydrogen [11] the proposed catalytic cycle is shown in Scheme 2.3. 

The dimerization of alkynes is a useful method for forming compounds such as enynes from simple alkynes [13]. The iridium-catalyzed dimerizahon of 1-alkyries was first reported by Crabtree, and afforded (Zj-head-to-head enynes using [Ir(biph)(PMe3)Cl] (biph = biphenyl-2,2 -diyl) as a catalyst [14]. Thereafter, an iridium complex generated in situ from [Ir(cod)Cl]2 and a phosphine ligand catalyzed the dimerizahon of 1-alkynes 1 to give (Tj-head-to-head enyne 2, fZj-head-to-head enyne 3, or 1,2,3-butatriene derivatives 4 in the presence of hiethylamine... 

Figure 1.25 exemplifies the strucmres of certain efficient precatalysts for asymmetric transfer hydrogenation of ketones. Precatalysts C1-C3 use the NH effect described above. A turnover frequency, defined as moles of product per mol of catalyst per hour, of 30,000 h is achieved by using of C2 and an alkaline base in 2-propanol. A Rh complex C3 is an isolobal to the corresponding arene-Ru complex (see Figure 1.23). The Ru complexes C4 " and C5 without NH group in ligand catalyze the reaction by different mechanisms. A higher than 90% optical yield is achieved by using C5 in reduction of certain aliphatic ketones.

Hydroboration and hydrosilylation reactions ofalkynes, when they do not proceed spontaneously, can be catalyzed by numerous transition metals [17]. Metal vinyli-dene-mediated processes uniquely provide (Z)-alkenes via trans-addition . In 2000, Miyaura and coworkers discovered that both Rh(I)- and Ir(I)-complexes supported by bulky electron-rich phosphine ligands catalyze the hydroboration of terf-butylacety-lene to give alkenylboronate 41 with >95 5 Z/E selectivity (Equation 9.5) [18]. 

Similarly, a water-soluble palladium complex of a sulfonated phenanthroline ligand catalyzed the highly selective aerobic oxidation of primary and secondary alcohols in an aqueous biphasic system in the absence of any organic solvent (Figure 1.8) [40]. The liquid product could be recovered by simple phase separation, and the aqueous phase, containing the catalyst, used with a fresh batch of alcohol substrate, affording a truly green method for the oxidation of alcohols. 

EDITOR S NOTE In 1982, J Halpem (University of Chicago) reported that rhodium complexes containing chiral phosphine ligands catalyze the hydrogenation of olefinic substrates such as alpha-aminoacrylic acid derivatives, producing chiral products with very high optical yields. 

Oxidation of Heteroatoms (N and S) 117 Table 3.9 Fe(acac)3-Schiff base ligand-catalyzed asymmetric oxidations. 

Correspondingly, the ligand-catalyzed reaction rate can be expressed in terms of a term expressing the relative coverage of site with L, 0L> such that... 

Figure 7.9. In a ligand-catalyzed reaction, the surface coraplexation with a bidentate ligand is followed by the rate-determining detachment of the metal ligand complex. [From Stumm (1986), with permission.]...

Figure 10. Complex 13 with two adjacent terminally bound ligands catalyzes the hydrolysis of dimethylformamide, giving formato-bridged complex 12.

Vanadium complexes of the first class of ligands catalyze the oxidation of bromide by hydrogen peroxide. These ligands (Figure 4) in-... 

Several Co complexes with chelating nitrogen ligands catalyze oxidation reactions, e.g. [CoII(bipy)2]2+ activates 02 and oxidizes N-methyl-anilines, benzyl alcohols, and aldehydes. In the absence of organic substrates 02 is reduced to H202.M Cobalt(II) complexes of tetraaza macrocyclic ligands (N4) reversibly form 02 adducts [(N4)CoOO]2+ which are rapidly reduced to [(N4)CoOOH]2+ these species are involved in the electro-reduction of 02 to H202.23... 

Nickel allyl complexes in the presence of chiral bidentate ligands catalyze the enantioselective codimerization of ethylene with norbornene and with styrene 129... 

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