Zirconocene, Zr-alkylated

Then, contrary to what was reported previously, the olefin dissociates from the zirconium metal complex. This conclusion was further supported by other experimental observations. However, it cannot be completely excluded that competition between dissociative and direct rearrangement pathways could occur with the different isomerization processes studied up to now. Note that with cationic zirconocene complexes [Cp2Zr-alkyl], DFT studies suggest that Zr-alkyl isomerizations occur by the classical reaction route, i.e. 3-H transfer, olefin rotation, and reinsertion into the Zr-H bond the olefin ligand appears to remain coordinated to the Zr metal center [89]. 

Scheme 1.7 Active-site counting method based on H-labelling, in the zirconocene-catalyzed polymerization of 1-hexene. Lower left typical NMR of the quenched polymer according to method A. The integrals allow the quantification of the Zr-alkyl active sites. All labels are found in the terminal position. Lower right comparison of fractional active-site counts using Method A (open circles, o) or Method B (diamonds ).

The aforementioned observations have significant mechanistic implications. As illustrated in Eqs. 6.2—6.4, in the chemistry of zirconocene—alkene complexes derived from longer chain alkylmagnesium halides, several additional selectivity issues present themselves. (1) The derived transition metal—alkene complex can exist in two diastereomeric forms, exemplified in Eqs. 6.2 and 6.3 by (R)-8 anti and syn reaction through these stereoisomeric complexes can lead to the formation of different product diastereomers (compare Eqs. 6.2 and 6.3, or Eqs. 6.3 and 6.4). The data in Table 6.2 indicate that the mode of addition shown in Eq. 6.2 is preferred. (2) As illustrated in Eqs. 6.3 and 6.4, the carbomagnesation process can afford either the n-alkyl or the branched product. Alkene substrate insertion from the more substituted front of the zirconocene—alkene system affords the branched isomer (Eq. 6.3), whereas reaction from the less substituted end of the (ebthi)Zr—alkene system leads to the formation of the straight-chain product (Eq. 6.4). The results shown in Table 6.2 indicate that, depending on the reaction conditions, products derived from the two isomeric metallacyclopentane formations can be formed competitively. 

In summary, zirconocene and half-sandwich zirconium-based catalysis has been developed both in surface and solution systems. In general, the activation of Zr-POSS and silica-supported zirconium system with MAO proved inappropriate (see silsesquioxane displacement and leaching, respectively, vide supra), while the acti-vahon with BArl proved more efficient, albeit structural rearrangement complicates the activation chemistry and simple Zr(IV) cationic alkyl species are seldom the outcome of the activation. 

In the zirconocene-catalyzed polymerization of alkenes, Landis and coworkers [20] have reported in situ observation of a Zr-polymeryl species, 15, at 233 K (Figure 1.5). Complex 15 is formed by partial reaction of 14 with excess 1-hexene. Derivatives 16 and 17 are generated quantitatively from 15 by addition of ca. 10 equiv. of propene and ethene, respectively. No other intermediates, such as alkene complexes, secondary alkyls, diasteromers of 15 or 16, or termination products, accumulate to detectable levels. These NMR studies permit direct monitoring of the initiation, propagation and termination processes, and provide a definitive distinction between intermittent and continuous propagation behavior. 

Neutral lanthanide complexes are convenient models for the cationic zirconocene systems and avoid complications due to the presence of counteranions and the limited solubility of ionic compounds. Dynamic NMR studies on yttrium complexes 44-46 has allowed the determination of the alkene binding enthalpy, the activation enthalpy of alkene dissociation, and the relative rates of dissociation and alkyl site exchange (site epimerisation) (Scheme 8.20). Compared to the Zr... 

Titanocene and zirconocene dichlorides (Cp2MtCl2 with Mt = Ti, Zr) were the first metallocenes studied [Breslow and Newburg, 1957 Natta et al., 1957a], The metallocene initiators, like the traditional Ziegler-Natta initiators, require activation by a Lewis acid coinitiator, sometimes called an activator. AIRCI2 and A1R3 were used initially, but the result was initiator systems with low activity for ethylene polymerization and no activity in a-olefin polymerization. The use of methylaluminoxane (MAO), [A1(CH3)0] , resulted in greatly improved activity for ethylene polymerization [Sinn and Kaminsky, 1980], The properties of MAO are discussed in Sec. 8-5g. MAO has two functions alkylation of a transition metal-chloride bond followed by abstraction of the second chloride to yield a metallocenium... 

The alkylation of the zirconocene thioacetaldehyde complex 81a with excess Mel also yielded an 5-methylated product (122) [Eq. (26)]. In contrast, the protonation by methanol in excess gave ethanethiol, trimethyl-phosphine, and dimethoxyzirconocene, presumably via a [Zr(OMe)(SEt) (t75-C5H5)2] intermediate.70... 

Zirconaindenes, which are easily obtained by insertion of various alkynes or an ynamine into the Zr—C bond of in situ generated99 100 benzyne-zirconocene, are very good precursors of 1,1-dichloro-l-germaindenes (90) (Scheme 16)101. This method has been successfully extended to tin chemistry (Scheme 17)102. In this case, a convenient reaction was obtained even with alkyl or aryltrichlorostannane. 

Besides hydrozirconation of terminal triple bonds Cp2Zr(H)Cl (16) also reacts with double bonds.8 The mechanism is similar to that described for alkynes. After coordination of alkene 5 to the Zr center giving -complex 23 the terminal double bond inserts into the Zr-H bond to form the stable (T-alkyl complex 24. The bulky zirconocene moiety again adds to the end-position of the terminal double bond. 

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