Titanium metallacyclobutane

At this point it should be noted that this mechanism is unexpected. Simple platinum alkyls decompose by 3-elimination whenever possible and there are no well-established examples of a-elimination [10]. All previous studies have indicated that metallacyclobutanes decompose by 3-elimination, even for tantalum and titanium derivatives for which a-elimination is a frequent mechanism for decomposition of the simple alkyls [11, 12]. There is even a labelling study which appears to prove the 3-elimination mechanism for decomposition of platinacyclobutanes (equation 3) [13]. 

Although the molybdenum and ruthenium complexes 1-3 have gained widespread popularity as initiators of RCM, the cydopentadienyl titanium derivative 93 (Tebbe reagent) [28,29] can also be used to promote olefin metathesis processes (Scheme 13) [28]. In a stoichiometric sense, 93 can be also used to promote the conversion of carbonyls into olefins [28b, 29]. Both transformations are thought to proceed via the reactive titanocene methylidene 94, which is released from the Tebbe reagent 93 on treatment with base. Subsequent reaction of 94 with olefins produces metallacyclobutanes 95 and 97. Isolation of these adducts, and extensive kinetic and labeling studies, have aided in the eluddation of the mechanism of metathesis processes [28]. 

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. 

A further way of generating carbon-metal double bonds is based on the [2 -I- 2] cycloreversion of metallacyclobutanes. This method has proven particularly useful for the generation of synthetically valuable titanium and zirconium carbene complexes (Section 3.1.7). 

Metallacyclobutane complexes of titanium began to make an appearance in 1980. [41-44] (A titanacycloZ Mfene complex was prepared from 3 in 1979. 

Tebbe found that titanocene complexes promoted olefin metathesis in addition to carbonyl olefination. Despite the fact that these complexes have low activity, they proved to be excellent model systems. For example, the Tebbe complex exchanges methylene units with a labeled terminal methylene at a slow rate that can be easily monitored (Eq. 4.6) [54]. This exchange is the essential transformation of olefin metathesis. When reactions with olefins are performed in the presence of a Lewis base, the intermediate titanium metallacycle can be isolated and even structurally characterized (Eq. 4.7) [61] These derivatives were not only the first metathesis-active metallacyclobutane complexes ever isolated, but they were also the first metallacyclobutanes isolated from the cycloaddition of a metal-carbene complex with an olefin. These metallacycles participate in all the reactions expected of olefin metathesis catalysts, especially exchange with olefins... 

The research by Beerman also demonstrated the relative stability of the Ti-methyl bond as compared to the relatively less stable Ti-ethyl bond that contains a hydrogen on the beta carbon and can, therefore, undergo beta-hydride transfer to the titanium metal and eliminate an ethylene molecule. This early research eventually lead in the 1970s to the identification of transition metal carbene complexes (M=CH2), which when reacted with olefins provide metallacyclobutanes [29]. 

In Cosee s mechanism [70], the stabilization of a titanium d orbital by interaction with an empty antibonding orbital of the alkene was suggested to be important for catalytic activity. There is no theoretical evidence for the d - tt back-donation [95]. Belov s binuclear active centers are ambiguous in light of the formation of metallacyclobutane and similar compounds [82-89]. The oxidation number of titanium is important in these reactions Ti(Ill) is known to be involved... 

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