Alkenes metal atoms

The alkene adsorbs to the catalyst surface, using its 7r bond to complex to the metal atoms. 

It should be noted that we have confined ourselves to the simplest reaction intermediates, namely, complexes involving only one transition metal atom and two alkene molecules. If the possibility of two transition metal atoms is taken into account the following complexes seem most likely ... 

For the catalyst system WCU-CsHbAICIs-CzHsOH, Calderon et al. (3, 22, 46) also proposed a kinetic scheme in which one metal atom, as the active center, is involved. According to this scheme, which was applied by Calderon to both acyclic and cyclic alkenes, the product molecules do not leave the complex in pairs. Rather, after each transalkylidenation step an exchange step occurs, in which one coordinated double bond is exchanged for the double bond of an incoming molecule. In this model the decomposition of the complex that is formed in the transalkylidenation step is specified, whereas in the models discussed earlier it is assumed that the decom-plexation steps, or the desorption steps, are kinetically not significant. 

Moving from alkenes to alkynes, it was found that a variety of transition-metal atoms react with hexafluoro-2-butyne (HFB) to form new... 

Transition-metal atoms have been shown to deoxygenate epoxides to alkenes (36). Chromium and titanium atoms emerged as the most effective species in this regard, abstracting over two equivalents of oxygen. By studying the reaction of a wide range of epoxides with chromium atoms, the reaction... 

Transition metal atoms react much more readily with alkenes than with alkanes because the initial interaction between the metal atom and an alkene is much less repulsive than for M+alkanes. To insert into a C-H bond of an alkane, the metal atom has to break a C-H bond and form an M-C and an M-H bond. The first step in a reaction with an alkene, however, is formation of a 7r-complex in which the C=C bond is merely weakened, not broken.119 The availability of the DCD bonding scheme (Sec. 1.1) leads... 

Note that although it may be possible for metal atoms to form a cr-complex with an alkane prior to insertion into a C-H bond, such complexes would be bound by only a few kcal/mol (comparable to dispersion forces), while metal-alkene 7r-complexes are typically bound by 20-60 kcal/mol. 

The actual spacings of the metal atoms in the surface will clearly be of importance in making one face of a metal crystal catalytically effective, and another not, depending on how closely the actual atom spacings approximate to the bond distances in alkene and hydrogen molecules. In practice only a relatively sma l proportion of the total metal surface is found to be catalytically effective—the so-called active points . These adsorb alkene strongly, and then desorb immediately the resultant alkane, thus becoming free for further alkene adsorption. 

The 1,3-dipolar cycloaddition of nitrones to vinyl ethers is accelerated by Ti(IV) species. The efficiency of the catalyst depends on its complexation capacity. The use of Ti( PrO)2Cl2 favors the formation of trans cycloadducts, presumably, via an endo bidentate complex, in which the metal atom is simultaneously coordinated to the vinyl ether and to the cyclic nitrone or to the Z-isomer of the acyclic nitrones (800a). Highly diastereo- and enantioselective 1,3-dipolar cycloaddition reactions of nitrones with alkenes, catalyzed by chiral polybi-naphtyl Lewis acids, have been developed. Isoxazolidines with up to 99% ee were obtained. The chiral polymer ligand influences the stereoselectivity to the same extent as its monomeric version, but has the advantage of easy recovery and reuse (800b). 

Intermediates corresponding to the coordination step are considered as sufficiently close to transition states of the insertion reaction, and hence as suitable preinsertion intermediates, only if the insertion can occur through a motion of the nuclei that is near to the least—principle of least nuclear motion.13,30,31 For instance, for alkene polymerizations preinsertion intermediates correspond to geometries with (a) a double bond of the olefin nearly parallel to the metal growing chain bond and (b) the first C-C bond of the chain nearly perpendicular to the plane defined by the double bond of the monomer and by the metal atom (50° < Gi < 130°, rather than 0i 180° see below). 

Prochirality Planar molecules possessing a double bond such as alkenes, imines, and ketones, which do not contain a chiral carbon in one of the side chains, are not chiral. When these molecules coordinate to a metal a chiral complex is formed, unless the alkene etc. has C2V symmetry. In other words, even a simple alkene such as propene will form a chiral complex with a transition metal. So will trans-2-butene, but cis-2-butene won t. If a bare metal atom coordinates to cis-2-butene the complex has a mirror plane, and hence the complex is not chiral. It is useful to give some thought to this and find out whether or not alkenes and hetero-alkenes form chiral complexes. One can also formulate it as follows complexation of a metal to the one face of the alkene gives rise to a certain enantiomer, and complexation to the other face gives rise to the other enantiomer. 

Initially, it was thought more likely that the electron poor metal atom would be involved in the electrophilic attack at the alkene and also the metal-carbon bond would bring the alkene closer to the chiral metal-ligand environment. This mechanism is analogous to alkene metathesis in which a metallacyclobutane is formed. Later work, though, has shown that for osmium the actual mechanism is the 3+2 addition. Molecular modelling lends support to the 3+2 mechanism, but also kinetic isotope effects support this (KIEs for 13C in substrate at high conversion). Oxetane formation should lead to a different KIE for the two alkene carbon atoms involved. Both experimentally and theoretically an equal KIE was found for both carbon atoms and thus it was concluded that an effectively symmetric addition, such as the 3+2 addition, is the actual mechanism [22] for osmium. 

The interaction of metal atoms with monoalkenes has been investigated on both a spectroscopic and preparative scale. It appears that the primary interaction between a metal atom and an alkene at low temperature is the formation of a ir-complex. This may subsequently lead to a thermally stable 7r-alkene complex or to rearrangement products by hydrogen abstraction or reaction with another alkene moiety, depending on the electronic requirements of the metal and the particular alkene considered. 

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