Oxidative addition and reductive elimination reactions

A very recent report moves forward significantly understanding the mechanism of reductive elimination reactions to form carbon-carbon bonds from platinum(IV) complexes.245 This report described the kinetics of reductive elimination from a cationic platinum(IV) complex as a function of solvent, of substituent character in a leaving group, of the potential effect of different spectator ligands and addressed whether there was a kinetic isotope effect. The reactions were studied also as a 

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Having established structural and electronic analogies between metal oxides and alkoxides of molybdenum and tungsten, the key remaining feature to be examined is the reactivity patterns of the metal-alkoxides. Metal-metal bonds provide both a source and a returning place for electrons in oxidative-addition and reductive elimination reactions. Stepwise transformations of M-M bond order, from 3 to 4 (37,38), 3 to 2 and 1 (39) have now been documented. The alkoxides M2(0R)6 (MiM) are coordinatively unsaturated, as is evident from their facile reversible reactions with donor ligands, eq. 1, and are readily oxidized in addition reactions of the type shown in equations 2 (39) and 3 (39). 

Fig. 23. Volume profile for the combined oxidative addition and reductive elimination reaction [PdMe2(bpy)] + Mel — [Pd(I)Me3(bpy)] — [Pd(I)Me(bpy)J + C2H6.

There are several pathways by which one ligand may replace another in a square planar complex, including nucleophilic substitution, electrophilic substitution, and oxidative addition followed by reductive elimination. The first two of these are probably familiar from courses in organic chemistry. Oxidative addition and reductive elimination reactions will be covered in detail in Chapter 15. All three of these classes have been effectively illustrated by Cross for reactions of PtMeCItPMe-Ph),.-... 

Attempts have been made to mimic proposed steps in catalysis at a platinum metal surface using well-characterized binuclear platinum complexes. A series of such complexes, stabilized by bridging bis(diphenyl-phosphino)methane ligands, has been prepared and structurally characterized. Included are diplati-num(I) complexes with Pt-Pt bonds, complexes with bridging hydride, carbonyl or methylene groups, and binuclear methylplatinum complexes. Reactions of these complexes have been studied and new binuclear oxidative addition and reductive elimination reactions, and a new catalyst for the water gas shift reaction have been discovered. 

Figure 2.6 Representative examples of oxidative addition and reductive elimination reactions.

Homobimetallic iridium(I) complexes containing the binucleating PNNP ligand undergo oxidative addition and reductive elimination reactions with acetyl chloride and methyl iodide. Thus,... 

A second major route to metal-metal complexes, related to the salt-elimination method described above, is elimination of neutral molecules with concurrent formation of metal-metal bonded complexes. Transihon metal hydrides readily undergo these dinuclear reductive elimination reactions. The oxidative addition/reductive elimination see Oxidative Addition and Reductive Elimination) reaction of molecular hydrogen is a key reachon in this area (equation 47). 

Oxidative-addition and reductive-elimination reactions of the group IIIB elements fall into two categories,... 

Oxidative Addition and Reductive Elimination Reactions at a Group IVB Metal Center... 

Oxidative-addition and reductive elimination reactions of transition metal complexes are crucial to many homogeneously catalyzed reactions and are important for bond formation. Reactant molecules such as H2 and Oj undergo oxidative addition to many transition metal centers. Oxidative addition of carbon-hydrogen bonds has been an active area of research. Reductive elimination is the process whereby products are eliminated from transition metal centers. 

Rhodium and iridium have provided the most important examples of oxidative addition and reductive elimination reactions. Rhodium complexes are among the most useful homogeneous catalysts. The more stable iridium complexes have been used to model oxidative addition and reductive elimination. 

Particular attention has been devoted to oxidative addition and reductive elimination reactions of [M2(PNNP)(/x-X)L2] with acyl and alkyl halides. Depending on the electron richness of the metals, a complete spectrum of possibilities was observed from reversible single oxidative addition on one of the metals to irreversible double oxidative addition on both metals (2) (Scheme 12). 

Related approaches were recently employed in mediating (stoichiometric) oxidative addition and reductive elimination reactions at cobalt centers bearing redox active ligands [7b, 7c, 25,34]. These reactions also proceed without a change in the d-electron configuration of the metal. 

The conversion of the Ir(III) cyclohexyl hydride complex to an Ir/cyclohexane system involves a change in the formal oxidation state of Ir from + 3 to +1 (i.e., a formal two-electron reduction). As a result, this elementary reaction step is generally called a reductive coupling (Chart 11.4). From a metal hydrocarbyl hydride complex (i.e., M(R)(H)), the overall process of C H bond formation and dissociation of free hydrocarbon (or related functionalized molecule) is called reductive elimination (Chart 11.4). The reverse process, metal coordination of a C—H bond and insertion into the C—H bond, is called oxidative addition. Note Oxidative addition and reductive elimination reactions are not limited to reactions involving C and H.)... 

The reaction of (Ph3P)3lrCl with l-Li-2-R-l,2-B,oC2Hio in Et20 leads to the formation of a carbaborane-iridium(i) complex, but this is unstable, and subsequent rapid oxidative-addition and reductive-elimination reactions occur (Scheme... 

Puddephatt etal. [41] have studied the C-H or C-C bond activation in the alkane complexes [PtMe(CH4)L2] or [PtMe(CHjCH3)L2] (L = NH3 or PH3) as well as the reductive elimination of methane or ethane from the five-coordinate model complexes [PtHMe2L2] or [PtMesLi], respectively, by carrying out extended Hiickel molecular orbital calculations and density functional theory. The oxidative addition and reductive elimination reactions occur by a concerted mechanism, probably with a pinched trigonal-bipyramidal complex on the... 

Oxidative addition and reductive elimination reactions play key roles in C—H activation reactions, where a strong C—bond is cleaved by a transition-metal complex. These are important reactions because they permit unfunctionalized hydrocarbons to be transformed into complex molecules. Bergman reported the following classic C—H reductive elimination/oxidative addition sequence. ... 

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