Alkenes complexation/insertion

One explanation for the regioselectivity is related to the stereochemistry of the diphosphine-Rh catalyst complexed with the alkene. We have seen earlier that high linear-to-branch ratios in Rh-catalyzed hydroformylation, as with Co-catalyzed hydroformylation, stem from the alkene complexation-insertion step of the catalytic cycle, so differences in steric and electronic factors as a function of stereochemistry could play a significant role in the regiochemical result of the reaction. There are two trigonal bipyramidal possibilities for the diphosphine-Rh-alkene complex, which are denoted a-e (apical-equatorial isomer 18) and e-e (diequatorial isomer 19). 

Initial step is the formation of a dicobalthexacarbonyl-alkyne complex 5 by reaction of alkyne 1 with dicobaltoctacarbonyl 4 with concomitant loss of two molecules of CO. Complex 5 has been shown to be an intermediate by independent synthesis. It is likely that complex 5 coordinates to the alkene 2. Insertion of carbon monoxide then leads to formation of a cyclopentenone complex 6, which decomposes into dicobalthexacarbonyl and cyclopentenone 3 ... 

These carbene (or alkylidene) complexes are used for various transformations. Known reactions of these complexes are (a) alkene metathesis, (b) alkene cyclopropanation, (c) carbonyl alkenation, (d) insertion into C-H, N-H and O-H bonds, (e) ylide formation and (f) dimerization. The reactivity of these complexes can be tuned by varying the metal, oxidation state or ligands. Nowadays carbene complexes with cumulated double bonds have also been synthesized and investigated [45-49] as well as carbene cluster compounds, which will not be discussed here [50]. 

The mechanism for the reaction catalyzed by cationic palladium complexes (Scheme 24) differs from that proposed for early transition metal complexes, as well as from that suggested for the reaction shown in Eq. 17. For this catalyst system, the alkene substrate inserts into a Pd - Si bond a rather than a Pd-H bond [63]. Hydrosilylation of methylpalladium complex 100 then provides methane and palladium silyl species 112 (Scheme 24). Complex 112 coordinates to and inserts into the least substituted olefin regioselectively and irreversibly to provide 113 after coordination of the second alkene. Insertion into the second alkene through a boat-like transition state leads to trans cyclopentane 114, and o-bond metathesis (or oxidative addition/reductive elimination) leads to the observed trans stereochemistry of product 101a with regeneration of 112 [69]. 

According to the general migratory-insertion mechanism proposed by Cossee,58 chain propagation (4.105) is a two-step process in which the precursor metal reagent (I) forms an intermediate alkene complex (II) that subsequently rearranges to the insertion product (III),... 

A prominent feature of this mechanism is that the growing polymer chain alternately swings between two r/.v-disposed coordination sites during each monomer insertion. General mechanistic outlines of this reaction have been extensively examined by large-scale computations and confirmed by experimental means.59 Our present goal is to clarify the localized donor-acceptor-orbital interactions that underlie (4.106), particularly the nature of the alkyl-alkene complex II. 

In addition to /3-H elimination, olefin insertion, and protonolysis, the cr-metal intermediate has also proved to be capable of undergoing a reductive elimination to bring about an alkylative alkoxylation. Under Pd catalysis, the reaction of 4-alkenols with aryl halides affords aryl-substituted THF rings instead of the aryl ethers that would be produced by a simple cross-coupling mechanism (Equation (126)).452 It has been suggested that G-O bond formation occurs in this case by yy/z-insertion of a coordinated alcohol rather than anti-attack onto a 7r-alkene complex.453... 

Oxidative addition of molecular hydrogen was considered to be involved in the alkyne hydrogenations catalyzed by [Pd(Ar-bian)(dmf)] complexes (4 in Scheme 4.4) [41, 42]. Although the mechanism was not completely addressed, 4 was considered to be the pre-catalyst, the real catalyst most likely being the [Pd(Ar-bian)(alkyne)] complex 18 in Scheme 4.11. Alkyne complex 18 was then invoked to undergo oxidative addition of H2 followed by insertion/elimination or pairwise transfer of hydrogen atoms, giving rise to the alkene-complex 19. 

Figure 6.1. Substrate-catalyst interactions favor a specific mode of alkene insertion into the zirconocene—alkene complex.

The aforementioned observations have significant mechanistic implications. As illustrated in Eqs. 6.2—6.4, in the chemistry of zirconocene—alkene complexes derived from longer chain alkylmagnesium halides, several additional selectivity issues present themselves. (1) The derived transition metal—alkene complex can exist in two diastereomeric forms, exemplified in Eqs. 6.2 and 6.3 by (R)-8 anti and syn reaction through these stereoisomeric complexes can lead to the formation of different product diastereomers (compare Eqs. 6.2 and 6.3, or Eqs. 6.3 and 6.4). The data in Table 6.2 indicate that the mode of addition shown in Eq. 6.2 is preferred. (2) As illustrated in Eqs. 6.3 and 6.4, the carbomagnesation process can afford either the n-alkyl or the branched product. Alkene substrate insertion from the more substituted front of the zirconocene—alkene system affords the branched isomer (Eq. 6.3), whereas reaction from the less substituted end of the (ebthi)Zr—alkene system leads to the formation of the straight-chain product (Eq. 6.4). The results shown in Table 6.2 indicate that, depending on the reaction conditions, products derived from the two isomeric metallacyclopentane formations can be formed competitively. 

Figure 2 shows the generally accepted dissociative mechanism for rhodium hydroformylation as proposed by Wilkinson [2], a modification of Heck and Breslow s reaction mechanism for the cobalt-catalyzed reaction [3]. With this mechanism, the selectivity for the linear or branched product is determined in the alkene-insertion step, provided that this is irreversible. Therefore, the alkene complex can lead either to linear or to branched Rh-alkyl complexes, which, in the subsequent catalytic steps, generate linear and branched aldehydes, respectively. 

The difference between this catalytic system and Wilkinson s catalyst lies in the sequence of the oxidative addition and the alkene complexation. As mentioned above, for the cationic catalysts the intermediate alkene (enamide) complex has been spectroscopically observed. Subsequently oxidative addition of H2 and insertion of the alkene occurs, followed by reductive elimination of the hydrogenation product. 

Insertion and -elimination. A catalytic cycle that involves only one type of elementary reaction must be a very facile process. Isomerisation is such a process since only migratory insertion and its counterpart P-elimination are required. Hence the metal complex can be optimised to do exactly this reaction as fast as possible. The actual situation is slightly more complex due to the necessity of vacant sites, which have to be created for alkene complexation and for P-elimination. 

Site control versus chain-end control. Over the years two mechanisms have been put forward as being responsible for the stereo-control of the growing polymer chain firstly the site-control mechanism and secondly the chain-end control mechanism. In the site control mechanism the structure of the catalytic site determines the way the molecule of 1-alkene will insert (enantiomorphic site control). Obviously, the Cossee mechanism belongs to this class. As we have seen previously, propene is prochiral and a catalyst may attack either the re-face or the, v/-facc. If the catalyst itself is chiral as the one drawn in Figure 10.2, a diastereomeric complex forms and there may be a preference for the... 

In the last decade an enormous revival of late transition catalysts for the polymerisation of alkenes has taken place [45] (remember that the first discovery of Ziegler for ethene polymerisation also concerned nickel and not titanium). The development of these catalysts is due to Brookhart in collaboration with DuPont (Figure 10.28) [46], Detailed low-temperature NMR studies have revealed the mechanism of the reaction [47], Interestingly, the resting state of the catalyst is the ethene-metal-alkyl complex and not the metal-alkyl complex as is the case for the ETM catalysts. For ETM catalysts the alkene complex intermediates are never observed. Thus, the migratory insertion is the rate-determining step (the turnover limiting step , in Brookhart s words) and the reaction rate is independent of the ethene concentration. 

A first indication of the likely geometry of zirconium(IV) alkene complexes was found in the crystallographically characterised alkyne insertion product 32 [72],... 

Under certain conditions, platinum alkene complexes can be converted to jr-allyl complexes by hydrogen loss (equation 281).860 Allyl alcohol insertion into a platinum(II) carbonyl bond gives an allyloxycarbonylplatinum(II) intermediate which can be decarboxylated to form the jj3-allyl complex (equation 282).861,863... 

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