Transitional metal-based catalysts

The number of branches in HDPE resins is low, at most 5 to 10 branches per 1000 carbon atoms in the chain. Even ethylene homopolymers produced with some transition-metal based catalysts are slightly branched they contain 0.5—3 branches per 1000 carbon atoms. Most of these branches are short, methyl, ethyl, and -butyl (6—8), and their presence is often related to traces of a-olefins in ethylene. The branching degree is one of the important stmctural features of HDPE. Along with molecular weight, it influences most physical and mechanical properties of HDPE resins. 

Extensive efforts have been made to develop catalyst systems to control the stereochemistry, addition site, and other properties of the final polymers. Among the most prominant ones are transition metal-based catalysts including Ziegler or Ziegler-Natta type catalysts. The metals most frequentiy studied are Ti (203,204), Mo (205), Co (206-208), Cr (206-208), Ni (209,210), V (205), Nd (211-215), and other lanthanides (216). Of these, Ti, Co, and Ni complexes have been used commercially. It has long been recognized that by varying the catalyst compositions, the trans/cis ratio for 1,4-additions can be controlled quite selectively (204). Catalysts have also been developed to control the ratio of 1,4- to 1,2-additions within the polymers (203). 

Several combinatorial approaches to the discovery of transition metal based catalysts for olefin polymerization have been described. In one study Brookhart-type polymer-bound Ni- and Pd-(l,2-diimine) complexes were prepared and used in ethylene polymerization (Scheme 3).60,61 A resin-bound diketone was condensed with 48 commercially available aminoarenes having different steric properties. The library was then split into 48 nickel and 48 palladium complexes by reaction with [NiBr2(dme)] and [PdClMe(COD)], respectively, all 96 pre-catalysts being spatially addressable. 

Carbonylation of unsaturated substrates has been known for decades but the reaction selectivity has been progressively improved by tuning the coordination sphere of late transition metal-based catalysts. Palladium assumes a privileged place in this chemistry and its versatility allows the use of mild conditions for the selective incorporation of CO into acyclic and cyclic compounds. Further improvements open a path to more sophisticated reactions, particularly cascade reactions. Similarly, asymmetric versions of most of these carbonylations can be envisioned. Atom economy and the green character of the process will probably be the key criteria for evaluating any new catalytic system. 

Early transition metal based catalysts react with a variety of polar substrates and impurities, except the molybdenum ones substituted electronically and sterically (Figure 16.12) in such a way that they become less oxophilic . In... 

On these transition metal-based catalysts, the selechve hydrogenahon of the C=0 group is very difficult because C=C double bond hydrogenahon is both thermodynamically and kinehcally favored, especially in the case of small molecules (e.g., acrolein, crotonaldehyde) where addihonal steric effects are not important [62, 71, 72]. 

Poly(l,3-butadiene)s with high 1,4-ds contents are valuable materials that have a wide range of applications as synthetic rubbers. A variety of transition metal-based catalysts have been investigated so far for the polymerization of... 

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). ... 

Several examples of transition metal-based catalysts supported via different approaches and located at different positions within various kinds of den-... 

Monomer coordination at the active site of the catalyst may occur in varied ways, essentially reducing to a twofold mechanism which is dependent on both the kind of monomer and the catalyst. This appears to encompass cases where unsaturated hydrocarbon monomers coordinate at the metal of transition metal-based catalysts, involving % complex formation, as well as cases where heterocyclic and heterounsaturated monomers are subjected to polymerisation with various coordination catalysts in which monomer complexation proceeds via a bond formation between the heteroatom and the metal atom. 

Coordination polymerisation via re complexes comprises polymerisation and copolymerisation processes with transition metal-based catalysts of unsaturated hydrocarbon monomers such as olefins [11-19], vinylaromatic monomers such as styrene [13, 20, 21], conjugated dienes [22-29], cycloolefins [30-39] and alkynes [39-45]. The coordination polymerisation of olefins concerns mostly ethylene, propylene and higher a-olefins [46], although polymerisation of cumulated diolefins (allenes) [47, 48], isomerisation 2, co-polymerisation of a-olefins [49], isomerisation 1,2-polymerisation of /i-olcfins [50, 51] and cyclopolymerisation of non-conjugated a, eo-diolefins [52, 53] are also included among coordination polymerisations involving re complex formation. 

The same group of coordination polymerisations in which alkene undergoes re complex formation with the metal atom includes the copolymerisation of ethylene, a-olefins, cycloolefins and styrene with carbon monoxide in the presence of transition metal-based catalysts [54-58], In this case, however, the carbon monoxide comonomer is complexed with the transition metal via the carbon atom. Coordination bond formation involves the overlapping of the carbon monoxide weakly antibonding and localised mostly at the carbon atom a orbital (electron pair at the carbon atom) with the unoccupied hybridised metal orbitals and the overlapping of the filled metal dz orbitals with the carbon monoxide re -antibonding orbital (re-donor re bond) [59], The carbon monoxide coordination with the transition metal is shown in Figure 2.2. 

Another type of metal-carbon bond, the metal carbene bond (with carbene of an electrophilic or nucleophilic character), appears to be the active bond in transition metal-based catalysts for the ring-opening metathesis polymerisation of cycloolefins. Such a bond, which is co-originated with metal by the sp2-hybridized carbon atom, possesses a a, n double bond character (Mt = C) [34,35], The enchainment of the coordinating cycloolefin at the active site... 

Various transition metal-based catalysts not containing preformed metal-carbon bonds have been developed for the polymerisation of conjugated dienes [27-35, 150-158]. These catalysts include monometallic precursors such as Rh, Co and Ni salts and bimetallic precursors such as C0CI2-AICI3. Some of them are soluble in a polymerisation medium, e.g. Rh(N03)3 in protic solvents (ROH, H2O) [27,150-154] and C0CI2—AICI3 in aprotic solvents [155-157], and some others are insoluble in a polymerisation diluent, e.g. TiCL—Ni(PCl3)4 [158]. 

The origin of the stereoregulation in conjugated diene coordination polymerisation was recognised by Porri et al. [7,41] who explained the different modes of formation of the isotactic and the syndiotactic polymers in the presence of various transition metal-based catalysts. 

Explain why polybutadienes obtained with rare-earth metal-based catalysts exhibit a higher degree of stereoregularity (higher contents of cis-1,4 monomeric units) than those derived from polymerisations in the presence of transition metal-based catalysts. 

On the other hand, aromatic monomers containing a boronic acid function apart from a halide function, i.e. haloarene boronic acids, undergo coordination homopolycondensation in the presence of transition metal-based catalysts, which results in the formation of poly(arylene)s [2] ... 

The carbonylation oxidative polycondensation of bisphenol, 2,2-bis(4-hydroxyphenyl)propane, with transition metal-based catalysts, which yields the respective aromatic polycarbonate, is of high potential interest [6] ... 

As stated above, the carbonylation oxidative polycondensation of bisphenol in the presence of transition metal-based catalysts leads to aromatic polycarbonate [scheme (18)] [6]. The reaction of bisphenol (HOArOH, e.g. Ar = p-C6H4 CMe2—C6H4—), carried out under CO and O2 pressure in a chlorohydrocarbon solvent under anhydrous conditions, using a group 8 metal-based catalyst (e.g. a PdBr2 complex) and a redox catalyst (e.g. Mn(II) (benzoinoxime)2, L vMn) in the presence of a base (e.g. 2,2,6,6,N-pentamethylpiperidine, R3N), involves most probably the pathway shown schematically below ... 

Catalytic alcoholysis of silanes by a variety of transition metal based catalysts is a useful method to form silyl ethers under mild conditions (Scheme 19). The process is atom-economical hydrogen gas is the only byproduct. This mild method has not been fully exploited for the preparation of unsymmetrical bis-alkoxysilanes. A catalytic synthesis using silicon alcoholysis would circumvent the need of bases (and the attendant formation of protic byproducts), and eliminate the need for excess silicon dichlorides in the first silyl ether formation. We sought catalytic methods that would ultimately allow formation of chiral tethers that are asymmetric at the silicon center (Scheme 20). Our method, once developed, should be easily transferable for use with high-value synthetic intermediates in a complex target-oriented synthesis therefore, it will be necessary to evaluate the scope and limitation of our new method. 

Oxidation of organic compounds in general and alkenes in particular is an enormous area, and transition-metal-based catalysts have played a pivotal role. Several books have summarized the state of the art.1 Historically, this has been an area in which empirical development of catalytic oxidation systems has outpaced mechanistic understanding. However, with the recent advent of new synthetic techniques, the number of well-characterized metal oxo compounds has expanded considerably in the past 15 years,2 and the prospect of understanding the behavior of the M=0 bond in reactions which create C—O bonds has drawn within reach. 

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