Titanocene, reactive

The polymers were converted to supported catalysts corresponding to homogeneous complexes of cobalt, rhodium and titanium. The cobalt catalyst exhibited no reactivity in a Fischer-Tropsch reaction, but was effective in promoting hydroformylation, as was a rhodium analog. A polymer bound titanocene catalyst maintained as much as a 40-fold activity over homogeneous titanocene in hydrogenations. The enhanced activity indicated better site isolation even without crosslinking. 

If 13 was allowed to stand at room temperature in an inert atmosphere over a prolonged period, or if a saturated hexane solution of Cp2TiMe2 was treated with excess hydrogen at low temperature with efficient stirring, a gray-green polymeric titanocene hydride 14 formed which exhibited reactivity similar to the violet hydride 13 (24). Thus, exposure of a toluene... 

A highly reactive form of titanocene could be obtained when a suspension of the gray-green hydride 14 was stirred in ethyl ether for 2 hours at room temperature. The solid gradually disappeared concurrent with the evolution of 0.5 equivalent of H2 per equivalent of Ti. Molecular weight measurements showed this metastable form of titanocene (15) to be dimeric. Treatment of a cold ethereal solution of (Cp2Ti)2 (15) with CO resulted in a quantitative yield of Cp2Ti(CO)2 (1) (24,36). 

Another extremely reactive form of titanocene, namely black tita-nocene, was discovered by Rausch and Alt in 1974 as the product of the photolysis of Cp2TiMe2 (19) in either aliphatic or aromatic solvents (41). Irradiation of a hexane solution of 19 resulted in the deposition of a dark precipitate with concomitant evolution of essentially only methane. Benzene solutions of this photochemically generated titanocene reacted rapidly with CO to give red solutions from which Cp2Ti(CO)2 (1) could be isolated in 60% yield. Similarly, 1 could be prepared directly under photochemical conditions in similar yield if 19 was irradiated in a CO atmosphere (41,42). 

Brintzinger and co-workers, while investigating the formation and chemical reactivity of various titanocenes, prepared a novel triphenyl-phosphine-titanocene complex of empirical formula [C10H10TiP(C6H5)3]2 (22) whose structure to date has been undetermined. The purple complex 22 can be prepared by the four routes illustrated below 24). 

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 nature of the substituent directly attached to the N-atom influences the properties (basicity, reduction potential, etc.) of the C = N function more than the substituents at the carbon atom. For example, it was found that Ir-dipho-sphine catalysts that are very active for N-aryl imines are deactivated rapidly when applied for aliphatic imines [7], or that titanocene-based catalysts are active only for N-alkyl imines but not for N-aryl imines [8, 20, 21]. Oximes and other C = N-X compounds show even more pronounced differences in reactivity. 

Collins and co-workers have also reported on an enantioselective catalytic Diels—Alder cycloaddition, in which zirconocene and titanocene bis(triflate) complexes were used as catalysts [104], The influence of the solvent polarity on the observed levels of stereoselectivity is noteworthy. For example, as shown in Scheme 6.34, with 108 as the catalyst, whereas in CH2C12 (1 mol% catalyst) the endo product was formed with 30% ee (30 1 endoxxo, 88% yield), in CH3N02 solution (5 mol% catalyst) the enantioselectivity was increased to 89% (7 1 endoxxo, 85% yield). Extensive 1H and 19F NMR studies further indicated that a mixture of metallocene—dienophile complexes was present in both solutions (-6 1 in CH2C12 and -2 1 in CH3N02, as shown in Scheme 6.34), and that most probably it was the minor complex isomer that was more reactive and led to the observed major enantiomer. For example, whereas nOe experiments led to ca. 5 % enhancement of the CpH proton signals of the same ring when Hb in the minor complex was irradiated, no enhancements were observed upon irradiation of Ha in the major complex. 

The general idea of this concept was first outlined by Nugent and Rajan-Babu [17-20] as shown in Scheme 3, and constitutes an analogue of the well-established opening of a cyclopropylcarbinyl radical [21,22]. Titanocenes have emerged as the most powerful reagents in these transformations. However, it is clearly attractive to find other metal complexes in order to develop novel reactivity patterns. 

An alternative, but related, route to allenic titanium reagents from propargylic esters has been reported recently. Reaction of titanocene dichloride with BuMgCl and Mg yields a reactive titanocene intermediate, formulated as Cp2Ti. This reduced Ti species reacts in situ by oxidative addition to propargylic acetates. The allenyltitanium reagents thus produced add to aldehydes and ketones, as expected, to afford homopropargylic alcohols (Table 9.27) [43]. 

Many of the metallocene compounds display unusual reactivities and reactions, of which none is more startling than the discovery by the Russian chemist, M. E. Vol pin, of absorption of dinitrogen, N2, by titanocene, (C5H3)2Ti, to form a complex or complexes that can be reduced easily to form ammonia. The nature of these complexes is in doubt, but very clear evidence has been obtained by J. E. Bercaw for the structure of the complex 9 formed from decamethylzirconocene and dinitrogen ... 

Further investigation of the equilibrium between titanacyclobutene and titanium vinyl alkylidene complexes, as discussed in Section 2.12.6.1.4, was reported recently <2007CEJ4074>, along with the incorporation of this reactivity pattern into the synthesis of conjugated dienes, homoallylic alcohols, vinylcyclopropanes, and phosphacyclobutenes from y-chloroallyl sulfides and a source of titanocene(ll). 

Bis(i -cyclopentadienyl)titanium or titanocene, (Tj-C5H5)2Ti (1), and bis(i7-cyclopentadienyl)zirconium or zirconocene, (i7-C5H5)2Zr (2), although frequently referred to in the literature, have never actually been isolated as discrete chemical compounds. However, these molecules have been implicated as highly reactive intermediates in a wide variety of chemical reactions with olefins, hydrogen, carbon monoxide, and dinitrogen. In recent years some discrete, well-characterized bis(7j-cyclopenta-dienyl) and bis(Tj-pentamethylcyclopentadienyl) complexes of low-valent titanium and zirconium have been isolated and studied, and it has become possible to understand some of the reasons for the remarkable reactivity of titanocene- and zirconocene-related organometallics toward small unsaturated molecules. 

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