Metallocyclobutanes, and

Another attempt to account for the differences between the behavior of platinum and palladium in bond shift isomerization has been presented in a recent review by Clarke and Rooney (2). This new mechanism, which is also based on the ability of platinum and not of palladium to promote the formation of metallocyclobutanes, derives from Rooney s earlier mechanism but replaces the cr-alky 1 precursor by a metallocyclobutane, and, in the transition state, the n-olefinic bonding by a zr-allylic bonding. As in the previous mechanism, it is assumed that on platinum the metallocyclobutane is formed directly, while in the case of palladium, it would result from a 12 hydrogen shift via a transient species of zi-allylic character (Scheme 28). 

From the above discussion, it ensues that a number of reactions involving carbon-carbon bond rupture and formation may be accounted for by a limited number of adsorbed species and elementary steps. The predominant precursor species in skeletal rearrangements are metallocyclobutanes and metallocarbenes, which can be further dehydrogenated to metallocarbynes. 

Fig. 9 Highlight of the intermediates of metallocyclobutane and alkylidene of the olefines metathesis with a W complex supported on silica. A pted with permission from the authors. ...

The formation of cyclopropanes from o(,P-unsaturated esters occurs under conditions at least as severe as those employed in the phosphine substitution and CO exchange reactions of carbene complexes. Coordinatively unsaturated carbene complexes are therefore reasonable intermediates for these reactions. Complexation of an alkene to the metal complex provides a means of bringing the carbene and alkene ligands into close proximity. Formation of a metallocyclobutane and reductive elimination of a cyclopropane complete our suggested mechanism (see Scheme 8). 

It should be noted that the equilibrium between a metallocyclobutane and a metal complex containing both an alkene and a carbene ligand provides a sufficient mechanism for olefin metathesis. Such a scheme has previously been proposed by Chauvin (Chauvin and Herrisson, 1971 Soufflet et al.. 

Green demonstrated (48) that a 7r-allyl complexed to W or Mo can undergo a nucleophilic attack by H- on the central carbon of the tj3 allylic group, forming a stable metallocyclobutane. [See Eq. (20).] Cyclopropane and propylene were evolved (49) on heating the metallocyclic... 

Osborn and Green s elegant results are instructive, but their relevance to metathesis must be qualified. Until actual catalytic activity with the respective complexes is demonstrated, it remains uncertain whether this chemistry indeed relates to olefin metathesis. With this qualification in mind, their work in concert is pioneering as it provides the initial experimental backing for a basic reaction wherein an olefin and a metal exclusively may produce the initiating carbene-metal complex by a simple sequence of 7r-complexation followed by a hydride shift, thus forming a 77-allyl-metal hydride entity which then rearranges into a metallocyclobutane via a nucleophilic attack of the hydride on the central atom of the 7r-allyl species ... 

As opinions regarding the metathesis reaction pathway have shifted in recent years to favor a nonpairwise carbene-to-metallocyclobutane transformation, increasing attention has been given to the mechanistic significance of cyclopropane olefin interconversions. This interconversion process seems to occur primarily when certain relatively inefficient catalysts are employed, which in itself raises questions. Under ideal conditions, "good metathesis catalysts are remarkably efficient promoters of transalkylidenation, and consequently are well suited for olefin and polymer syntheses. Thus, most early studies focused primarily on applications. When side reactions did occur, they were usually ignored or presumed to be trivial cationic processes. 

Several studies now exist which add credence to Casey s attractive proposal that metallocyclobutanes intervene in metathesis and cyclopro-panation reactions. Additionally, metallocyclobutanes have been observed to interconvert to propylene derivatives by way of /3-hydrogen transfer reactions. It is not well established, however, whether precoordination of the reacting olefin is required in all these processes. The proposed interrelation of these reactions may be formally presented as follows ... 

Reaction pathways apparently analogous to d and f of Eq. (26) yield a mixture of propylene and cyclopropane. Only when photochemical activation was employed were the major products olefins derived from metathesis-decomposition of the metallocycle. The failure to form metathesis olefins under moderate conditions is significant. It may be that either unimolecular dissociation of the olefin from the complex (in the absence of excess olefin to restabilize the carbene) is energetically unfavored, or the metallocyclobutane structure in the equilibrium given by steps a and b in Eq. (26) is highly stabilized and favored. These results... 

Metallocyclobutanes from cyclopropanes have been frequently invoked in transition metal-catalyzed rearrangements of strained ring hydrocarbons, and this body of chemistry is quite rich and diverse, as evidenced in the excellent review by Bishop (72). Because of this diversity, the significance of isolated observations should not be overstated nevertheless, certain reactions outlined by Bishop are closely related to the carbene retroadditions reported by Gassman and co-workers using metathesis catalysts. 

Soluble metathesis catalysts yield trans products in reactions with // / v-2-pentene, but generally are not very stereospecific with c/.v-2-pen-tene. In the latter case, the initially formed butenes and hexenes are typically about 60 and 50% cis, respectively. Basset noted (19) that widely diverse catalyst systems behaved similarily, and so it was suggested that the ligand composition about the transition metal was not a significant factor in the steric course of these reactions. Subsequently, various schemes to portray the stereochemistry have been proposed which deal only with interactions involving alkyl substituents on the reacting olefin or on the presumed metallocyclobutane intermediate. 

To explain the observed rupture of sterically-hindered substituted tertiarysecondary C-C bond on these low dispersed Pt catalysts, a third mechanism was proposed that competes with the dicarbene mechanism.55 This third mechanism involves a metallocyclobutane species as an intermediate. In fact, both McVicker et al.11 and Coq et al.56 have cited the metallocyclobutane mechanism as responsible for the observed hydrogenolysis of 1,2,4-trimethylcyclohexane and 2,2,3,3-tetra-methylbutane, respectively. 

Initiation involves coordination of the double bond of monomer with the transition metal (imino and OR ligands not shown), cleavage of the 7t-bond with formation of a 4-membered metallocyclobutane intermediate, followed by rearrangement to form a metal-carbene propagating center ... 

Scheme 2. Schematic relationships between C2 hydrocarbon adsorbates and the surface species that could be derived from them. Possible relationships are indicated between surface species that involve not more than one addition/subtraction of H and/or M atoms. Strong bonding of these species to metal atoms could give rise to structures approximating to metallocyclopropanes or metallocyclopropenes, respectively. These structures with C=C or C = C groupings frequently occur on surfaces with additional n bonds to further metal atoms, M in other cases, two additional CM bonds may replace a CC double bond. JOn surfaces the metal atoms are usually bonded to each other so that the analogous molecular cluster compounds would be metallocyclopropanes or metallocyclobutanes, etc. 1 See footnote to Scheme I. The dashed rectangles indicate surface species that involve no CH bond breaking on adsorption of the parent hydrocarbon. These are most likely to be present under low-temperature adsorption conditions.

Two resonance-contributing structures (3a and 3b), in the formalism of ylide structures, can be used to describe metal carbene intermediates. The highly electrophilic character of those derived from Cu and Rh catalysts suggests that the contribution from the metal-stabilized carbocation 3b is important in the overall evaluation of the reactivities and selectivities of these metal carbene intermediates. Emphasis on the metal carbene structure 3a has led to the subsequently discounted proposal that cyclopropane formation from reactions with alkenes occurs through the intervention of a metallocyclobutane intermediate [18]. The metal-stabilized carbocation structure 3b is consistent with the cyclopropanation mechanism in which LnM dissociates from the carbene as bond-formation occurs between the carbene and the reacting alkene (Eq. 5.4) [7,15]. 

The extensive data accumulated by Nakamura and Otsuka, although interpreted by them as being due to the intervention of metal carbene and metallocyclobutane intermediates, can also be rationalized by an alternative mechanism in which coordination of the chiral Co(II) catalyst with the alkene activates the alkene for electrophilic addition to the diazo compound (Scheme 5.4). Subsequent ring closure can be envisioned to occur via a diazonium ion intermediate, without involving at any stage a metal carbene intermediate. 

Akeypart in the analysis and proposal was electron accountancy - on the basis of the usual propensity for the adoption of a noble gas outer shell configuration - and all of the proposed intermediates have 16- or 18-electron configurations except the metallocyclobutane (26) in pathway II which has 14. On this basis, one might expect that pathway I, the non-dissociative pathway, would predominate over pathway II. In the presence of a large excess of Cy3P, which was used only to simplify the kinetic analysis, this is clearly the case. However, under the... 

The product from reaction 7.14 has been isolated and fully characterized. This lends credence to the mechanistic postulate that metallocyclobutane rings play a crucial role in metathesis reactions. 

The catalytic cycle proposed for the rhodium-porphyrin-based catalyst is shown in Fig. 7.18. In the presence of alkene the rhodium-porphyrin precatalyst is converted to 7.69. Formations of 7.70 and 7.71 are inferred on the basis of NMR and other spectroscopic data. Reaction of alkene with 7.71 gives the cyclopropanated product and regenerates 7.69. As in metathesis reactions, the last step probably involves a metallocyclobutane intermediate that collapses to give the cyclopropane ring and free rhodium-porphyrin complex. This is assumed to be the case for all metal-catalyzed diazo compound-based cyclo-propanation reactions. 

More than half a century ago it was observed that Re207 and Mo or W carbonyls immobilized on alumina or silica could catalyze the metathesis of propylene into ethylene and 2-butene, an equilibrium reaction. The reaction can be driven either way and it is 100% atom efficient. The introduction of metathesis-based industrial processes was considerably faster than the elucidation of the mechanistic fundamentals [103, 104]. Indeed the first process, the Phillips triolefin process (Scheme 5.55) that was used to convert excess propylene into ethylene and 2-butene, was shut down in 1972, one year after Chauvin proposed the mechanism (Scheme 5.54) that earned him the Nobel prize [105]. Starting with a metal carbene species as active catalyst a metallocyclobutane has to be formed. The Fischer-type metal carbenes known at the time did not catalyze the metathesis reaction but further evidence supporting the Chauvin mechanism was published. Once the Schrock-type metal carbenes became known this changed. In 1980 Schrock and coworkers reported tungsten carbene complexes... 

His proposal involved a metal carbene and a metallocyclobutane intermediate and was the first proposed mechanism consistent with all experimental observations to date. Later, Grubbs and coworkers performed spectroscopic studies on reaction intermediates and confirmed the presence of the proposed metal carbene. These results, along with the isolation of various metal alkyli-dene complexes from reaction mixtures eventually led to the development of well-defined metal carbene-containing catalysts of tungsten and molybdenum [23-25] (Fig. 2). After decades of research on olefin metathesis polymerization, polymer chemists started to use these well-defined catalysts to create novel polymer structures, while the application of metathesis in small molecule chemistry was just beginning. These advances in the understanding of metathesis continued, but low catalyst stability greatly hindered extensive use of the reaction. 

Chen QM/MM (2a) and (4a) Ligand shape (phosphine vs. NHC) is linked to rate of dissociation of trans phosphine. Phosphine dissociation is always slow step for (4a) while metallocyclobutane formation is the energetic barrier for (2a)... 

Catalysts comprising a metal-carbon double bond (metallocarbenes, or metallocenes) are efficient. With these initiators, the polymerization mechanism appears to involve coordination of the C=C double bond in the cycio- or dicycloalkene at a vacant d orbital on the metal. The metallocyclobutane intermediate which is formed decomposes to produce a new metal carbene and a new C=C bond. Propagation consists of repealed insertions of cycloalkenes at the metal carbene. 

The mechanism for olefin metathesis is complex, and involves metal-carbene intermediates— intermediates that contain a metal-carbon double bond. The mechanism is drawn for the reaction of a terminal alkene (RCH=CH2) with Grubbs catalyst, abbreviated as Ru=CHPh, to form RCH = CHR and CH2 = CH2. To begin metathesis, Grubbs catalyst reacts with the alkene substrate to form two new metal-carbenes A and B by a two-step process addition of Ru=CHPh to the alkene to yield two different metallocyclobutanes (Step [1]), followed by elimination to form A and B (Steps [2a] and [2b]). The alkene by-products formed in this process (RCH=CHPh and PhCH=CH2) are present in only a small amount since Grubbs reagent is used catalytically. 

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