Group 4 metal benzyl catalysts

Some of the vinyl monomers polymerized by transition metal benzyl compounds are listed in Table IX. In this table R represents the rate of polymerization in moles per liter per second M sec-1), [M]0 the initial monomer concentration in moles per liter (M) and [C]0 the initial concentration of catalyst in the same units. The ratio i2/[M]0[C]0 gives a measure of the reactivity of the system which is approximately independent of the concentration of catalyst and monomer. It will be observed that the substitution in the benzyl group is able to affect the polymerization rate significantly, but the groups that increase the polymerization rate toward ethylene have the opposite effect where styrene is concerned. It would also appear that titanium complexes are more active than zirconium. The results with styrene and p-bromostyrene suggests that substituents in the monomer, which increase the electronegative character of the double bond, reduces the polymerization rate. The order of reactivity of various olefinically unsaturated compounds is approximately as follows ... 

It is more difficult to study equilibria between transition metal allyl compounds and bases, olefins, etc. In the case of Zr (allyl) 4 and pyridine, a valency change occurs as shown by Eq. (8), and the process is irreversible. The polymerization is considered to be preceded by displacement of one allyl group by the monomer (12) as shown in Eq. (1). In the methyl methacrylate/Cr(allyl)3 system it was not possible to detect any interaction between the olefin and catalyst with infrared radiation, even with equimolar concentrations because of the strong absorption by the allyl groups not involved in the displacement processes. Due to the latter, evidence for equilibrium between monomer and catalyst is less likely to be found with these compounds than with the transition metal benzyl compounds. 

Benzyl groups can be removed hydrogenolytically with a transition metal as catalyst. 

Metal and Metal Oxide Catalysts. Only a few examples are known on application of metal and metal oxide catalysts for carbonylation reaction. For example, it has been reported that benzyl alcohol could be carbonylated with CO to phenylacetic acid (with 100% selectivity) in the presence of rhodium metal Rh(0) (72). Methyl formate was prepared by treatment of CH3OH with CO in the presence of alkali earth metal oxide catalysts. The oxide catalysts are preferably CaO catalysts supported on oxides of group Ila (except Ca), Ilb, Ilia, or IVa metals. CH3OH was autoclaved with CaO/ZnO under 50 atm of CO at 180°C for 2 h to give 9.7% of methyl formate at 99.9% selectivity (73). 

The importance of the o-hydroxyl moiety of the 4-benzyl-shielding group of R,R-BOX/o-HOBn-Cu(OTf)2 complex was indicated when enantioselectivities were compared between the following two reactions. Thus, the enantioselectivity observed in the reaction of O-benzylhydroxylamine with l-crotonoyl-3-phenyl-2-imi-dazolidinone catalyzed by this catalyst was 85% ee, while that observed in a similar reaction catalyzed by J ,J -BOX/Bn.Cu(OTf)2 having no hydroxyl moiety was much lower (71% ee). In these reactions, the same mode of chirality was induced (Scheme 7.46). We believe the free hydroxyl groups can weakly coordinate to the copper(II) ion to hinder the free rotation of the benzyl-shielding substituent across the C(4)-CH2 bond. This conformational lock would either make the coordination of acceptor molecules to the metallic center of catalyst easy or increase the efficiency of chiral shielding of the coordinated acceptor molecules. 

Hydrogenolysis of halides and benzylic groups presumably involves intermediates formed by oxidative addition to the active metal catalyst to generate intermediates similar to those involved in hydrogenation. The hydrogenolysis is completed by reductive elimination.58 Many other examples of this pattern of reactivity are discussed in Chapter 8. 

The use of weakly coordinating and fluorinated anions such as B(C6H4F-4)4, B(C6F5)4, and MeB(C6F5)3 further enhanced the activities of Group 4 cationic complexes for the polymerization of olefins and thereby their activity reached a level comparable to those of MAO-activated metallocene catalysts. Base-free cationic metal alkyl complexes and catalytic studies on them had mainly been concerned with cationic methyl complexes, [Cp2M-Me] +. However, their thermal instability restricts the use of such systems at technically useful temperatures. The corresponding thermally more stable benzyl complexes,... 

As shown in the previous two sections, rhodium(n) dimers are superior catalysts for metal carbene C-H insertion reactions. For nitrene C-H insertion reactions, many catalysts found to be effective for carbene transfer are also effective for these reactions. Particularly, Rh2(OAc)4 has demonstrated great effectiveness in the inter- and intramolecular nitrene C-H insertions. The exploration of enantioselective C-H amination using chiral rhodium catalysts has been reported by several groups.225,244,253-255 Hashimoto s dirhodium tetrakis[A-tetrachlorophthaloyl-(A)-/ r/-leuci-nate], Rh2(derived rhodium complex, Rh2(i -BNP)4 48,244 afforded moderate enantiomeric excess for amidation of benzylic C-H bonds with NsN=IPh. 

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