Iridium complexes carbonates

In 1963 Vaska 164) discovered that the iridium complex Ir(PPh3)2C (CO) takes up molecular oxygen reversibly with 1 1 stoichiometry. This complex has since been shown to reversibly sorb (1 1) ethylene (755), carbon dioxide (765), F2C=CF2 and F3C—C=C—CF3 (767), as well as various other ligands (765). Ibers md La Placa (769)... 

Remarkable carbon-boron bond-forming reactions are catalyzed by iridium complexes and proceed at room temperature with excellent regioselectivity, governed by steric factors. Heteroarenes are borylated in the 2-position and this reaction is generally tolerant of halide substituents on the arene (Equations (87) and (88)). 

A two-component bimetallic catalytic system has been developed for the allylic etherification of aliphatic alcohols, where an Ir(i) catalyst acts on allylic carbonates to generate electrophiles, while the aliphatic alcohols are independently activated by Zn(n) coordination to function as nucleophiles (Equation (48)).194 A cationic iridium complex, [Ir(COD)2]BF4,195 and an Ru(n)-bipyridine complex196 have also been reported to effectively catalyze the O-allylation of aliphatic alcohols, although allyl acetate and MeOH, respectively, are employed in excess in these examples. 

The phosphoramidite ligands that are the focus of the remainder of this chapter have prompted the investigation of ligands containing related structures. Iridium complexes of aspartic acid-derived P-chirogenic diaminophosphine oxides (DlAPHOXs) catalyze the amination [62] and alkylation [63] of aUyhc carbonates (Scheme 6). With BSA as base and catalytic amounts of NaPFs as additive, branched amination and alkylation products were obtained from cinnamyl carbonates in excellent yields and enantioselectivities. However, the yields and enantios-electivities were lower for the reactions of alkyl-substituted aUyhc carbonates. Added LiOAc increased the enantioselectivities of aUyhc alkylation products. 

Carreira et al. reported the kinetic resolution of branched allylic carbonates catalyzed by an iridium complex derived from a chiral [2.2.2]-bicyclooctadiene [48]. Reactions of allylic carbonates with phenol were run to 50% conversion of the carbonate, leaving unreacted allylic carbonate in high enantiomeric excess (Scheme 32). The phenyl ether products were also isolated in mid-to-high enantiomeric excess. 

This chapter reviews an overview of the iridium-complex-catalyzed crosscoupling reachons to form carbon-carbon and carbon-heteroatom bonds [12],... 

Platinum complexes have been mainly used in the hydrosilylation of carbon-carbon bonds, and ruthenium complexes in the metathesis and silylative coupling of olefins with vinylsilanes. Most of these processes (except for olefin metathesis) may also proceed efficiently in the presence of rhodium and iridium complexes. 

Among the latter group, iridium complexes (though less common than rhodium) and perhaps also ruthenium play crucial roles in many of the above-mentioned transformations of silicon compounds, leading to the creahon of sihcon-carbon bonds. Examples include the hydrosilylation or dehydrogenahve silylation of alkenes and alkynes, the hydroformylahon of vinylsilanes, and the silyhbrmylation of alkynes as well as activation of the sp C—H of arenes (by disilanes) and alkenes (by vinylsilanes). 

By contrast, the isomerization of silyl olefins and addition of silylacetylenes =C—H bond into imines catalyzed by iridium complexes appears to serve as a suitable route for the synthesis of silylfunctionahzed organic compounds. Hence, the acquisition of experimental data on catalysis by iridium complexes in silicon chemistry may be regarded as an initial stage in the quest for catalytic processes leading to the synthesis of other p-block (e.g. B, Ge, Sn, P)-carbon bond-containing compounds. 

The LUMO in d pentatetraenylidene complexes is predominantly localized on the odd carbon atoms and to a lesser extent on the metal. The coefficients on Cl and C3 are very similar, independent of the metal-ligand fragment and the terminal substituent. The coefficient at C5 is somewhat larger. In square-planar d rhodium and iridium complexes the coefficient at the metal is comparable to that on C5 and is larger than those on Cl and C3. Thus, a nucleophilic attack at the metal of d complexes has also to be taken into account. 

Rasmussen, S.C., Richter, M.M., Yi, E., Place, H. and Brewer, KJ. (1990) Synthesis and characterization of a series of novel rhodium and iridium complexes containing polypyridyl bridging ligands Potential uses in the development of multimetal catalysts for carbon dioxide reduction. Inorg. Chem., 29, 3926—3932. 

Among the catalysts used are Lewis acids991 and phosphine-nickel complexes.992 Certain of the reverse cyclobutane ring openings can also be catalytically induced (8-40). The role of the catalyst is not certain and may be different in each case. One possibility is that the presence of the catalyst causes a forbidden reaction to become allowed, through coordination of the catalyst to the -it or a bonds of the substrate.993 In such a case the reaction would of course be a concerted 2S + 2S process. However, the available evidence is more consistent with nonconcerted mechanisms involving metal-carbon a-bonded intermediates, at least in most cases.994 For example, such an intermediate was isolated in the dimerization of nor-bornadiene, catalyzed by iridium complexes.995... 

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