Zirconium amidate

The synthesis, structures, and reactivity of neutral and cationic mono- and bis(guanidinato)zirconium(rV) complexes have been studied in detail. Either salt-metathesis using preformed lithium guanidinates or carbodiimide insertion of zirconium amides can be employed. Typical examples for these two main synthetic routes are illustrated in Schemes 73 and 74. Various cr-alkyl complexes and cationic species derived from these precursors have been prepared and structurally characterized. 

Acidic transition-metal hydrides have been used to prepare metal-silicon bonded compounds by an interesting condensation reaction that proceeds with amine elimination (equation 30)66. An attempt to carry out a similar reaction between Ph3SiH and the zirconium amide Cp2Zr(NMe2)2 failed67. 

Organozirconium cations and lanthanide amide complexes initiate the ring-opening polymerization of s-caprolactone, due to the highly electropositive nature of the metal. The zirconium amide 59 was able to polymerize s-caprolactone to the polylactone by ring-opening polymerization. THE... 

Wood MC, Leitch DC, Yeung CS, Kozak JA, Schafer LL. Chiral neutral zirconium amidate complexes for the asymmetric hydroamination of alkenes. Angew. Chem. Int. Ed. 2007 46(3) 354-358. 

Amides, Imides, Alkamides. When zirconium tetrachloride reacts with hquid ammonia, only one chloride is displaced to form a white precipitate, insoluble in hquid ammonia (227) ... 

The zirconium—nitrogen bond is weaker than the zirconium—oxygen bond even under anhydrous conditions. When zirconium tetrachloride reacts with carbonyl-containing amides such as... 

With (Z)-amide enolates and (Z)-thioamide enolates a strong preference for sm-adducts is also observed. In general, boron or zirconium (Z)-enolates of ketones and amides display a higher simple diastereoselectivity in favor of syn-products than the corresponding lithium or magnesium enolates6,7. 

Thus, jyn-adducts arise predominantly, as expected, according to the Zimmerman-Traxier model. Provided that either boron or zirconium is the enolate-metal atom, high syn selectivity is achieved. The total amount of anti-adducts is lower than 2% in the case of amides 1 and 2, and it approaches zero when the other reagents arc used94 . The induced stereoselectivities are impressive for the amides and remarkable in the case of the imides. 

Note also the stereochemistry. In some cases, two new stereogenic centers are formed. The hydroxyl group and any C(2) substituent on the enolate can be in a syn or anti relationship. For many aldol addition reactions, the stereochemical outcome of the reaction can be predicted and analyzed on the basis of the detailed mechanism of the reaction. Entry 1 is a mixed ketone-aldehyde aldol addition carried out by kinetic formation of the less-substituted ketone enolate. Entries 2 to 4 are similar reactions but with more highly substituted reactants. Entries 5 and 6 involve boron enolates, which are discussed in Section 2.1.2.2. Entry 7 shows the formation of a boron enolate of an amide reactions of this type are considered in Section 2.1.3. Entries 8 to 10 show titanium, tin, and zirconium enolates and are discussed in Section 2.1.2.3. 

Other examples of this synthetic strategy are known for example, a recent zirconium polymer by Illingsworth and Burke (8), who joined amine side groups of a zirconium bis(quadridentate Schiff-base) with an acid dianhydride to give amide linkages. Once again, caution is necesary, as Jones and Power (2) learned when they attempted to link metal bisO-diketonates) with sulfur halides that is, they obtained insoluble metal sulfides because the p-diketone complexes which they used were fairly labile and the insolubility drove the reactions to completion in the wrong direction. 

Zirconium bis(amides) such as (35) and (36) display moderate ethylene polymerization activities.133,134 Complex (37) containing a chelating diamide ligand has been shown to initiate the living polymerization of a-olefins such as 1-hexene (Mw/Mn= 1.05-1.08) with activities up to 750gmmol-1 h-1.135-137 The living polymerization of propylene using this system activated with... 

Dianionic bis(amide) ligands bearing additional donor atoms have been described by several researchers. High activities for ethylene polymerization are observed for pyridyldiamido zirconium complexes such as (42) (1,500gmmol-1 bar-1 h-1),145 although the corresponding titanium complex is much less active.146... 

A similar method has been described by Badia and co-workers who used chiral amides derived from pseudoephe-drine.139 Moreover, a zirconium-mediated Claisen-aldol tandem reaction of an a,cr-dialkylated ester with several aldehydes has been reported (Scheme 39).140 After the initial Claisen condensation, zirconium enolate intermediate 92 reacts with various types of aldehydes through aldol-type reaction and subsequent lactonization, providing the corresponding pyran-2,4-diones. 

As with the above pyrrolidine, proline-type chiral auxiliaries also show different behaviors toward zirconium or lithium enolate mediated aldol reactions. Evans found that lithium enolates derived from prolinol amides exhibit excellent diastereofacial selectivities in alkylation reactions (see Section 2.2.32), while the lithium enolates of proline amides are unsuccessful in aldol condensations. Effective chiral reagents were zirconium enolates, which can be obtained from the corresponding lithium enolates via metal exchange with Cp2ZrCl2. For example, excellent levels of asymmetric induction in the aldol process with synj anti selectivity of 96-98% and diastereofacial selectivity of 50-200 116a can be achieved in the Zr-enolate-mediated aldol reaction (see Scheme 3-10). 

An illustrative example of a simple amide is provided by the structure of the zirconium dimethylamide in Figure 6.1, which shows that it is dimerized through two bridging-NMe2 ligands whereas in the vapor phase it has a monomeric structure with tetrahedrally coordinated zirconium. The dimeric structure may also be contrasted with that of [Ti(NMe2)4] which is a monomer in the crystal phase. ... 

The use of supporting amido ligands for transition metal based catalysts was intensified by reports of the use of bidentate amide donors of type V, with titanium and zirconium " (the related ligand W is also known). ... 

Metal dialkylamides were reviewed by Bradley in 1972.61 A comprehensive list of all zirconium and hafnium amides reported prior to 1979 may be found in the book by Lappert et al.62... 

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