Transition elements alkyls

Silicon-transition metal chemistry is a relatively new area. The work of Hein and his associates (1941) on Sn—Co derivatives established the possibility of forming bonds between a Group IVB metal and a transition element 139), but it was another fifteen years before CpFe(CO)2SiMej 203), the first of many silyl derivatives, was synthesized. The interest in these compounds derives from (1) comparison with the corresponding alkyl- and Ge-, Sn-, and Pb- transition metal (M) complexes, including the role of ir-back-bonding from filled d orbitals of M into empty d orbitals on Si (or other Group IVB metal), and (2) expectation of useful catalytic properties from such heteronuclear derivatives. 

A thermally robust dihapto C02 complex was easily obtained according to equation (62).631 Complex (46) is the first authentic (X-ray diffraction) C02 complex of a hard oxophilic early transition element. The C02 (C—O bond lengths 1.283(8) and 1.216(8) A) lies close to the alkyl group, but its orientation is such that its insertion into the metal-alkyl bond would produce the unfavored metallacarboxylate ester instead of a carboxylato complex. 

ZIEGLER-NATTA POLYMERIZATION. Polymerization of vinyl monomers under mild conditions using aluminum alkyls and TiCL lor other transition element halide) catalyst to give a stereoregulated, or tactic, polymer. These polymers, in which the stereochemistry of the chain is not random have very useful physical properties. 

The conversion of CO + H2 (syn-gas) to hydrocarbons and oxygenates (Fischer-Tropsch chemistry)119 is of considerable industrial importance and recently the activation and fixation of carbon monoxide in homogeneous systems has been an active area for research.120,121 The early transition elements and the early actinide elements, in particular zirconium124 and thorium,125 126 supported by two pentamethylcyclopentadienyl ligands have provided a rich chemistry in the non-catalytic activation of CO. Reactions of alkyl and hydride ligands attached to the Cp2M centers with CO lead to formation of reactive tf2-acyl or -formyl compounds.125,126 These may be viewed in terms of the resonance forms (1) and (2) shown below. 

Ziegler catalysis involves rapid polymerization of ethylene and a-ole-fins with the aid of catalysts based on transition-element compounds, normally formed by reaction of a transition-element halide or alkoxide or alkyl or aryl derivative with a main-group element alkyl or alkyl halide (1,2). Catalysts of this type operate at low pressures (up to 30 atm), but often at 8-10 atm, and, in special cases, even under reduced pressure, and at temperatures up to 120°C, but often as low as 20-50°C. Approximately 2,200,000 tons of polyethylene and 2,900,000 tons of polypropylene are produced per year with the aid of such catalysts. The polyeth-... 

Using diolefins and carefully selected Ziegler-type catalysts, it has been possible to obtain the 1,4-c/s-, the 1,4-trans-, and the 1,2-polybutadienes more than 98% pure. In the case of polyisoprene, the 3,4-structure is produced. There are thousands of patents involving every combination of pure or mixed main-group alkyls with transition-element compounds, each claiming advantages. However, compositions containing titanium, vanadium, chromium, and, in special cases, molybdenum, cobalt, rhodium, and nickel are primarily used. 

Two notable points from the aforegoing discussion are as follows. (1) By far the majority of the known monohalogenoalkyl compounds are of the group VTII transition elements there are very few early transition metal halogenoalkyl compounds known. (2) Very few monofluoroalkyl metal complexes have been prepared. The lack of early transition metal halogenoalkyl compounds may be in part due to the high electropositivity of these metals, which facilitates a- and / -elimination reactions. Related hydride elimination reactions almost certainly occur more easily for early transition metal alkyl compounds than for later transition metal compounds. In this regard it is particularly noteworthy that one of the only early transition metal haloalkyl compounds mentioned is the fluoroethyl scandium com-... 

When carbon monoxide is bonded to a transition element, in a positively charged or even uncharged compound, the electrophilic capacity of carbon increases compared with the isolated molecule. Examples of nucleophilic attack are in equations (4) and (5). The reaction of methyl-lithium with W(CO)e giving the anioiuc acyl complex of equation (4a) is followed by alkylation to the carbene derivative of equation (4b). The formation of a carbamoyl complex with m-PtCl2(CO)2 is shown in equation (5). 

As a third-row transition element, iridium does have a propensity to attain higher oxidation states than the first and second row congeners. Thus, it is possible to isolate and study a variety of Ir(V) alkyl compounds. ... 

Metal oxide catalysts can be classified as oxides of transition elements or as oxides of other typical metals. Typical transition elements include Cr, Fe, Co, Mo, and V, whose oxides catalyze oxidation and reduction reactions by changing the oxidation state of the metal ion. For selective oxidation of hydrocarbons, mixed oxides containing Mo and V are widely used. Oxides of other metals (acidic oxides such as silica and silica-alumina, basic oxides such as CaO and MgO, and amphoteric oxides such as alumina) catalyze acid or base reactions such as alkylation, isomerization, and hydration-dehydration. 

Reaction (a) requires that the metal be less electropositive than A1—a requirement met by most transition elements. Reaction (b) requires that a vacant coordination site be available (the olefin produced by /3-hydrogen elimination must be at least transiently coordinated ), and that the alkyl group possess at least one /S-hydrogen . 

The two-component catalytic systems used for olefin polymerization (Ziegler-Natta catalysts) are combinations of a compound of a IV-VIII group transition metal (catalyst) and an organometallic compound of a I-III group non-transition element (cocatalyst) An active center (AC) of polymerization in these systems is a compound (at the surface in the case of solid catalysts) which contains a transition metal-alkyl bond into which monomer insertion occurs during the propagation reaction. In the case of two-component catalysts an AC is formed by alkylation of a transition metal compound with the cocatalyst, for example ... 

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