Zr-complex

Ziegler polymerization catalysts may be prepared from Cp—Zr complexes and tri alkyl aluminum. The molecular weight of the polymers can be controlled over a wide range by varying the temperature. The activity of these catalysts is considerably increased by the addition of small amounts of water (263,264) (see Olefin polya rs). 

The reactivity of the Cp (L)Ir=PMes (L=PPh3, CO) phosphinidene complexes is much less diverse than those with Zr. Only the formation of phosphaalkenes has been observed in the reaction with CH2I2 and CHI3 [102]. This reduced reactivity of the Ir complexes as compared to Zr complex 53 has been... 

The role of coordinated ethylene is evidenced by the recent ab initio calculation performed by Espelid and Borve [121-123], who have shown that ethylene may coordinate in two different ways to the reduced Cr(II) species, either as a molecular complex or covalently bound to chromium. At longer Cr-C distances (2.36-2.38 A) an ethylene-chromium zr-complex forms, in which the four d electrons of chromium remain high-spin coupled and the coordination interaction is characterized by donation from ethylene to chromium. Cr(II) species in a pseudo-tetrahedral geometry may adsorb up to two equivalents of ethylene. In the case of a pseudo-octahedral Cr(II) site a third ethylene molecule can also be present. The monoethylene complex on the pseudo-tetrahedral Cr(II) site was also found to undergo a transformation to covalently bound complex, characterized by shorter Cr-C distances (about... 

Hydrozirconation of terminal alkynes R-C=CH (R= aryl, alkyl) with 1 affords terminally ( )-Zr-substituted alkenes with high efficiency and excellent stereochemical and regiochemical control (>98%). These alkenylzirconocene complexes are of particular interest for synthetic use [136, 143, 144]. Moreover, beside the electropositive halogen sources [145] and heteroatom electrophiles [3] used in the pioneering studies to directly cleave the Zr-C bond, ( )-vinyl-Zr complexes were recently transformed into a number of other trans-functionalized alkenes such as ( )-vinyl-sul-fides[146], vinylic selenol esters [147], vinyl-sulfones [148], vinyl-iodonium [149], vinyl-(R0)2P(0) [150], and vinilic tellurides [143]. 

Molybdenum allyl complexes react with surface OH groups to produce catalysts active for olefin metathesis.34 35 Using silica as a support for the heterog-enization of Ti and Zr complexes for the polymerization of ethylene did not give clear results.36 In these cases, HY zeolite appeared to be a more suitable support. The comparable productivity of the zeolite-supported catalyst with... 

Wipf and coworkers used a Claisen rearrangement of allyl phenyl ethers 4-309 followed by an enantioselective carboalumination using the chiral Zr-complex 4-310 and trimethyl aluminum (Scheme 4.67) [104]. After an oxidative work-up of the intermediate trialkylalane, the corresponding alcohols 4-311 were obtained with up to 80% ee and 78% yield. One can also transfer an ethyl group using triethyl aluminum with even better ee-values (up to 92%), but the yields were rather low (42%) due to a more sluggish oxidative cleavage of the Al-C bond. 

Ti-BINOL-catalyzed reactions have been well established. When the Ti is replaced by Zr,92 the resulting complex 140 can also catalyze the addition of allyl-tributyltin to aldehydes (aldehydes allyl-tributyltin 140 = 1 2 0.2 mol ratio) in the presence of 4 A MS. Product l-alken-4-ols are obtained in good yield and high ee. The, Sz-face of the aldehyde is attacked if (S)-BINOL is used, and Re-face attack takes place when (K)-BINOL is used as the chiral ligand. For Zr complex-catalyzed reactions, the reaction proceeds much faster, although the... 

The high levels of enantioselectivity obtained in the asymmetric catalytic carbomagnesa-tion reactions (Tables 6.1 and 6.2) imply an organized (ebthi)Zr—alkene complex interaction with the heterocyclic alkene substrates. When chiral unsaturated pyrans or furans are employed, the resident center of asymmetry may induce differential rates of reaction, such that after -50 % conversion one enantiomer of the chiral alkene can be recovered in high enantiomeric purity. As an example, molecular models indicate that with a 2-substituted pyran, as shown in Fig. 6.2, the mode of addition labeled as I should be significantly favored over II or III, where unfavorable steric interactions between the (ebthi)Zr complex and the olefmic substrate would lead to significant catalyst—substrate complex destabilization. 

Scheme 6.12. Enantioselective carbo-aluminations of unactivated alkenes are promoted by neutral (37) and cationic (38 + B(C6F5)3) chiral Zr complexes.

Erker and co-workers reported in 1990 that in the presence of the chiral Zr complex 82, shown in Eq. 6.16, 1-naphthol adds to ethyl pyruvate with an appreciable level of enantio-... 

The reactive nature of compound 22 is illustrated by the series of transformations shown in Scheme 7.12, in which its Zr—C bond reacts selectively with electrophilic reagents to produce a-haloboronates 36—38. Compound 22 also catalyzes the polymerization of styrene. The polymers thus obtained had weight-average molecular masses in the range 75000—100000 with polydispersities of 1.8—2.1. An X-ray analysis of 22 confirmed it to be a four-coordinate Zr complex with two cyclopentadienyl rings, chlorine, and the aliphatic C-l carbon atom as the ligands (Fig. 7.4). 

Vinylboronates are generally less reactive than vinylzirconocenes towards various electrophiles and hence selective reactions of the latter should be possible. It was found that selective cleavage of the carbon—zirconium bond in 45 by N-halosuccinimides provides (a-haloalkenyl)boronic esters 53 in excellent chemical yields and with complete re-gioselectivity (Scheme 7.17) [54], An X-ray crystal structure determination of 45 confirmed the configuration of the four-coordinate Zr complex, with two cyclopentadienyl rings, Cl, and C(sp2) as the four ligands (Fig. 7.5) [54,126]. 

Figure 7.9. X-ray crystal structure of the Ga/Zr complex 112. The carbon atom C-2 is planar tetracoordinate. Adapted by the authors.

SCHEME 14.7 Reaction energies (in kcal/mol) at the B3LYP/LANL2DZ level of theory between various intermediates of the reaction of Ti and Zr complexes where L = H. The energetics with L — Cl also gives similar trend in the order of the relative energies [1 lb,c]. The values in normal font correspond to M = Ti and values in parenthesis correspond to M = Zr. (Reproduced from Jemmis, E.D. and Giju, K.T., J. Am. Chem. Soc., 120, 6952, 1998. With permission.)... 

Metal complexes of pinene-fused boratabenzene ligands, analogous to chiral metallocenes that have found application in catalysis and enantioselective synthesis, have been prepared.122-124 With late transition metals such as Mn and Fe, the complexes are obtained as mixtures of diastereomers (e.g., 97) with the sterically less congested exo form predominating, but the bis(ligand) Zr complex 98 was obtained as the pure exo,exo product.124 A lithium... 

Rearrangement to the diphenyline product 3, formally a forbidden [3,5] shift, must take place by a different mechanism in parallel to 2 formation. Previous mechanistic suggestions have attempted to explain the formation of both products within the same mechanistic framework. It is now apparent that 3 is formed by rate-limiting N-N bond fission to give an intermediate from which the product is formed. The nature of this intermediate is not yet known, but it has been suggested16 that it could be a zr-complex. 

In the isoelectronic series (butadiene)M( j8 — CgHg) (M = Ti, Zr, Hf), the Hf complex exhibits an NMR spectrum at > 30 °C consistent with an envelope flip (AG = 17.6 kcalmol-1). The same process can be detected for the Zr complex at > 40 °C only via magnetization transfer experiments (AG > 20 kcalmol-1). The Ti complex exhibits a static structure by NMR spectroscopy16. 

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