Metallacyclobutane complexes reactions

Fig. 30. Mechanism for C-C activation of propene. Decay of the allyl hydride complex may proceed via migration of the metal-bound H atom to the /3-carbon atom in the allyl moiety (i.e. reverse /3-H migration), leading to formation of the same metallacyclobutane complex implicated in the Y + cyclopropane reaction. The dynamically most favorable decay pathway is to YCH2 + C2H4.

The expected intermediate for the metathesis reaction of a metal alkylidene complex and an alkene is a metallacyclobutane complex. Grubbs studied titanium complexes and he found that biscyclopentadienyl-titanium complexes are active as metathesis catalysts, the stable resting state of the catalyst is a titanacyclobutane, rather than a titanium alkylidene complex [15], A variety of metathesis reactions are catalysed by the complex shown in Figure 16.8, although the activity is moderate. Kinetic and labelling studies were used to demonstrate that this reaction proceeds through the carbene intermediate. 

Over the past 15 years the understanding of the mechanism of these reactions has been greatly enhanced through the preparation of metal carbene complexes, particularly of Mo, W and Ru, that are both electronically unsaturated (<18e) and coordinatively unsaturated (usually <6 ligands), and which can act directly as initiators of olefin metathesis reactions. The intermediate metallacyclobutane complexes can also occasionally be observed. Furthermore, certain metallacyclobutane complexes can be used as initiators. 

Intermediate molybdacyclobutane complexes have also been detected in the reactions of 7 with 21-24115. Only in the case of 21 is the ultimate product a long-chain polymer, but in all cases one may observe, at 0-60 °C, a clean first-order rearrangement of the initial metallacyclobutane complex to the first metal carbene adduct, consisting of an equilibrium mixture of syn and anti rotamers in the ratio 9 1 (see below). Except in the case of 21, the metal carbene complexes do not survive for very long. For 21, however, ROMP is propagated, and distinct H NMR signals are seen for the longer-chain metal carbene complexes in both syn and anti forms. 

It has generally been assumed that in olefin metathesis reactions the olefin first coordinates to the metal carbene complex, en route to the formation of the intermediate metallacyclobutane complex, and that after cleavage of this intermediate the newly formed double bond is temporarily coordinated to the metal centre. A number of stable metal-carbene-olefin complexes are known see elsewhere116,117 for earlier references. They are mostly stabilized by chelation of the olefin and/or by heteroatom substituents on the carbene, although some have been prepared which enjoy neither of these modes of stabilization118,119. 

The cycloaddition of alkenes with metal alkylidene complexes remains the most common entry into the metallacyclobutane structural class. Consistent with metallacyclobutane intermediacy in the olefin metathesis reaction, the [2+2] cycloaddition is generally reversible a propensity for cycloreversion (Section 2.12.6.2.4), however, can significantly limit the utility of metallacyclobutane complexes as intermediates in other synthetic transformations. 

Despite dramatically different ancillary ligand sets, two distinct niobium and tantalum alkylidene systems provide isolable metallacyclobutanes upon reaction with ethylene. In one case, the tantalum aryldiamine pincer complex 148 reacts with ethylene to provide the cr-trimethylsilyltantalacyclobutane complex 149 (Equation 66) <19940M3259>. In a more comprehensive study, alkadiene-supported half-sandwich alkylidene complexes of both tantalum and niobium (the former isolable, the latter generated in situ) undergo [2+2] cycloaddition with a range of acyclic and cyclic alkenes, albeit in modest isolated yield (Equation 67). 

Other active methylene compounds also react with both palladium(ll) <2002POL2653> and gold(m) <1997JOM243> to produce metallacyclobutane complexes (Scheme 34). The gold complex is not sufficiently stable for isolation. In these reactions, the silver oxide functions both as a base and a reagent for halide abstraction. In the gold series, 1,1,3,3-tetracyanopropane is also a competent pro-nucleophile <1999JOM219>. 

More recent developments in the mechanistic aspects of the alkene metathesis reaction include the observation that the alkene coordinates to the metal carbene complex prior to the formation of the metallacyclobutane complex. Thns a 2 - - 2 addition reaction of the alkene to the carbene is very unlikely, and a vacant coordination site appears to be necessary for catalytic activity. It has also been shown that the metal carbene complex can exist in different rotameric forms (equation 11) and that the two rotamers can have different reactivities toward alkenes. " The latter observation may explain why similar ROMP catalysts can produce polymers that have very different stereochemistries. Finally, the synthesis of a well-defined Ru carbene complex (equation 12) that is a good initiator for ROMP reactions suggests that carbenes are probably the active species in catalysts derived from the later transition elements. ... 

The above results suggest that the metallacyclobutane complexes 48-51 have at least two photodecomposition pathways available to them (1) r -r shift of the Cp rings with homolysis of one of the metal-carbon bonds, and (2) possibly a concerted, photoinduced reductive-elimination reaction for the formation of cyclopropylbenzene from 51 [Eq. (63)]. 

Likewise, the organic products of the reaction between Ta(CHCMe3)Cl3L2 (L = py, THF) and ethylene issue from )5-hydrogen transfer (4,4-dimethylpentene) but also contain the metathesis product 3,3-dimethyl-l-butene. Unlike phosphine derivatives, these latter complexes react with cis-2-pentene to give exclusively the metathesis olefins and act as catalysts for the metathesis of cis-2-pentene. Thus, the presence of a hard ligand and the formation of an intermediate a,a jS-trisubstituted metallacyclobutane complex do not favor jS-hydrogen transfer ... 

The initial observation of a metal carbene that reacted with an alkene to give a metallacyclobutane complex was reported by Osborn and coworkers for the reaction shown in equation (10). This reaction was observed by NMR spectroscopy at low temperature (—70°C). When this reaction mixture was allowed to warm to higher temperature, polynorbornene was produced in high yield. Shortly after this discovery, the titanocene complex (4) was shown to be an efficient catalyst for the synthesis of monodisperse polynorbornenes. These discoveries, along with the synthesis of a new family of tungsten (5a), molybdenum (5b), and rhenium (6) catalysts,shown in Figure 1, have opened a new era of ROMP chemistry in which the polymer synthesis is guided by the selection of a catalyst... 

The most important advance over the past 15 years has been the preparation of numerous well-defined metal carbene complexes which can act directly as initiators of all types of olefin metathesis reaction. These second-generation catalysts allow much closer control and better understanding of the mechanism of the olefin metathesis reaction. The initiating and propagating species can be closely monitored and in some cases the intermediate metallacyclobutane complexes can also be observed. Well-defined metallacyclobutane complexes also can sometimes be used as initiators. 

We have seen from Fig. 3.4 that some initiator remains after all the monomer has reacted with W(=CHCMe3)(Br)2(OCH2CMc3)2/GaBr3. This is still the case when the initiator and monomer are mixed at —78°C in CD2CI2 confirming that this is not due to inefficient mixing. If the temperature is raised slowly, reaction begins at about -53°C but the initial spectra are different from those observed at room temperature. The species formed at low temperature have been identified as intermediate transoid metallacyclobutane complexes 7. 

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