Elimination reactions transition metal complexes

Reductive elimination on transition metal complexes seems to be enhanced by coordination of electron-withdrawing 71-acids such as cyanobenzene and cyanoethylene. For example, the reductive elimination reaction of NiR2(bpy) (R=alkyl or aryl group bpy =2,2 -bipyridyl) is enhanced by electron-withdrawing olefinic and aromatic compounds [12-16] (Scheme 1). 

The ability of a reaction intermediate such as Cr(CO)5 to bind methane may be counterintuitive but commands attention for its significance in relation to C-H bond activation, a teasing but vital issue in the context of the chemical industry (118). Numerous complexes of alkanes with unsaturated transition-metal fragments (including atoms and ions) have now been detected in both the gas and condensed phases. It is not surprising that all of them are unstable at room temperature. Experiments in which alkanes undergo oxidative addition to, or reductive elimination from, transition-metal complexes have revealed, nonetheless, the intermediacy of alkane complexes. 

The reductive elimination represents the reverse reaction of oxidative addition and constitutes the last elementary reaction in the general catalytic cycle. Catalyst regeneration and liberation of the desired cross coupling product are typically obtained at the same time during this step. Since the reductive elimination from transition metal complexes is the reverse reaction of the oxidative addition, involving the same transition states, the principles described in Sect. 1.3 prevail, although in opposite direction (Scheme 1.15). As a consequence, the underlying... 

Pd-cataly2ed reactions of butadiene are different from those catalyzed by other transition metal complexes. Unlike Ni(0) catalysts, neither the well known cyclodimerization nor cyclotrimerization to form COD or CDT[1,2] takes place with Pd(0) catalysts. Pd(0) complexes catalyze two important reactions of conjugated dienes[3,4]. The first type is linear dimerization. The most characteristic and useful reaction of butadiene catalyzed by Pd(0) is dimerization with incorporation of nucleophiles. The bis-rr-allylpalladium complex 3 is believed to be an intermediate of 1,3,7-octatriene (7j and telomers 5 and 6[5,6]. The complex 3 is the resonance form of 2,5-divinylpalladacyclopentane (1) and pallada-3,7-cyclononadiene (2) formed by the oxidative cyclization of butadiene. The second reaction characteristic of Pd is the co-cyclization of butadiene with C = 0 bonds of aldehydes[7-9] and CO jlO] and C = N bonds of Schiff bases[ll] and isocyanate[12] to form the six-membered heterocyclic compounds 9 with two vinyl groups. The cyclization is explained by the insertion of these unsaturated bonds into the complex 1 to generate 8 and its reductive elimination to give 9. 

The general mechanism of coupling reactions of aryl-alkenyl halides with organometallic reagents and nucleophiles is shown in Fig. 9.4. It contains (a) oxidative addition of aryl-alkenyl halides to zero-valent transition metal catalysts such as Pd(0), (b) transmetallation of organometallic reagents to transition metal complexes, and (c) reductive elimination of coupled product with the regeneration of the zero-valent transition metal catalyst. 

Two closely related reactions, (a) and (b), illustrated by Eq. (12) (Rj = HPhj, Etj, Phj, CI3, CljPh) and (13), of silicon hydrides with transition metal complexes generate compounds with Si—M bonds with elimination of hydrogen (a) cleavage of metal-metal bonds and (b) reaction with transition metal hydrides. Reactions discussed in this section are relevant to... 

Besides dissociation of ligands, photoexcitation of transition metal complexes can facilitate (1) - oxidative addition to metal atoms of C-C, C-H, H-H, C-Hal, H-Si, C-0 and C-P moieties (2) - reductive elimination reactions, forming C-C, C-H, H-H, C-Hal, Hal-Hal and H-Hal moieties (3) - various rearrangements of atoms and chemical bonds in the coordination sphere of metal atoms, such as migratory insertion to C=C bonds, carbonyl and carbenes, ot- and P-elimination, a- and P-cleavage of C-C bonds, coupling of various moieties and bonds, isomerizations, etc. (see [11, 12] and refs, therein). 

The mechanism for the reaction catalyzed by cationic palladium complexes (Scheme 24) differs from that proposed for early transition metal complexes, as well as from that suggested for the reaction shown in Eq. 17. For this catalyst system, the alkene substrate inserts into a Pd - Si bond a rather than a Pd-H bond [63]. Hydrosilylation of methylpalladium complex 100 then provides methane and palladium silyl species 112 (Scheme 24). Complex 112 coordinates to and inserts into the least substituted olefin regioselectively and irreversibly to provide 113 after coordination of the second alkene. Insertion into the second alkene through a boat-like transition state leads to trans cyclopentane 114, and o-bond metathesis (or oxidative addition/reductive elimination) leads to the observed trans stereochemistry of product 101a with regeneration of 112 [69]. 

Whereas most of the known silylamines containing both a silicon halogen and nitrogen hydrogen unit undergo rapid condensation with HC1 elimination [11], transition metal substitution of the silicon provides unexpected high thermal stability. Compounds of this type are available via reaction of the dichlorosilyl complexes 18a-c with bulky primary amines to generate 19a-c (Eq. (4)). 

The reaction of bis(silanethiolato) complexes of group 10 metals with transition metal complexes gives the corresponding multinuclear complexes accompanied by the elimination of the silyl chloride (Scheme 14).117,118... 

Transition metal complex-catalyzed carbon-nitrogen bond formations have been developed as fundamentally important reactions. This chapter highlights the allylic amination and its asymmetric version as well as all other possible aminations such as crosscoupling reactions, oxidative addition-/3-elimination, and hydroamination, except for nitrene reactions. This chapter has been organized according to the different types of reactions and references to literature from 1993 to 2004 have been used. 

Cycloaddition refers to a process of unsaturated moieties forming a metallacyclic compound. It is sometimes categorised under oxidative additions, but we prefer this separate listing. Examples of the process are presented in Figure 2.22. Metal complexes which actually have revealed these reactions are M = L2Ni for reaction a, M = Cp2Ti for reactions b and c, M = Ta for d, and M = (RO)3W for e. The latter examples involving metal-to-carbon multiple bonds have only been observed for early transition metal complexes, the same ones mentioned under a-elimination, 2.20. 

In the present chapter, no explicit discussion or review of the acid-and/or base-catalyzed isomerization of olefins will be included. The discussion will be confined to isomerizations achieved with soluble transition metal complexes. However, it will be seen that addition and elimination reactions and allylic intermediates figure prominently in discussions of the mechanisms. 

A more familiar example is Sn2 addition of an anionic nucleophile to an alkyl halide. In the gas phase, this occurs without activation energy, and the known barrier for the process in solution is a solvent effect (see discussion in Chapter 6). Finally, reactions of electron-deficient species, including transition-metal complexes, often occur with little or no energy barrier. Processes as hydroboration and 3-hydride elimination are likely candidates. 

Support-bound transition metal complexes have mainly been prepared as insoluble catalysts. Table 4.1 lists representative examples of such polymer-bound complexes. Polystyrene-bound molybdenum carbonyl complexes have been prepared for the study of ligand substitution reactions and oxidative eliminations [51], Moreover, well-defined molybdenum, rhodium, and iridium phosphine complexes have been prepared on copolymers of PEG and silica [52]. Several reviews have covered the preparation and application of support-bound reagents, including transition metal complexes [53-59]. Examples of the preparation and uses of organomercury and organo-zinc compounds are discussed in Section 4.1. 

Ammonium dithiocarbamates can be prepared through reaction (11). With HC1 or H2S04 at lower temperatures the free acids are formed. Only one transition metal complex (37) is known, with a pseudo-octahedral coordination of Ni four sulfur atoms of the dithiocarbamate in the equatorial plane and two pyridine solvent molecules at the apical positions. Sulfides can be eliminated from monosubstituted dithiocarbamates to give isothiocyanates.53... 

A number of transition metal complexes react with alkenes, alkynes and dienes to afford insertion products (see Volume 4, Part 3). A general problem is that the newly formed carbon-metal bond is usually quite reactive and can undergo a variety of transformations, such as -hydride elimination or another insertion reaction, before being trapped by an electrophile.200 Usually, a better stability and lower reactivity is observed if the first carbometallation step leads to a metallacycle. It is worthy to note that the carbometallation of perfluorinated alkenes and alkynes constitutes a large fraction of the substrates investigated with transition metal complexes.20015... 

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