Vinyl complex

It has been established that alkoxy alkenylcarbene complexes participate as dienophiles in Diels-Alder reactions not only with higher rates but also with better regio- and stereoselectivities than the corresponding esters [95]. This is clearly illustrated in Scheme 51 for the reactions of an unsubstituted vinyl complex with isoprene. This complex reacts to completion at 25 °C in 3 h whereas the cycloaddition reaction of methyl acrylate with isoprene requires 7 months at the same temperature. The rate enhancement observed for this complex is comparable to that for the corresponding aluminium chloride-catalysed reactions of methyl acrylate and isoprene (Scheme 51). 

Wakatsuki et al. (4) proposed vinyl complex, 5, and presented DFT results supporting isomerization to a vinylidene hydride as the rate determining step. Our results indicate that the rate determining step involves H-OH bond breaking and that protonation of a bound alkyne is the rate determining step in this... 

To probe the possibility that rrfl/wo/d-2-metalla-l,3-butadiene species (like 47) would spontaneously rearrange to 17-allyl products (like 48) via interligand C—C coupling, the Fe-vinyl complex 50 was treated first with methyllithium and then with benzoyl chloride [Eq. (14)] (57). Attack by... 

If an excess of allene is used, two allenes are incorporated in the jr al lyl complex formed. The latter complex, 71, is formed via a trapping of a vinyl complex 70 (Scheme 15). 

Recently, Ohe and IJemura reported a novel approach to the catalytic cyclopropanation of alkenes via 2-furyl178 179 or 2-pyrrolyl carbenoids180 that originate from the intramolecular nucleophilic attack of a carbonyl oxygen or an imine nitrogen (ene-yne-ketone and ene-yne-imine precursor, respectively) on a 7t-alkyne complex or a cationic cr-vinyl complex. Initially, the group 6 complexes like Cr(CO)s were used. Soon it was found that a series of late transition... 

In another study the kinetics and mechanism of an unprecedented T/2-vinyl isomerization of a highly fluorinated tungsten(II) metalla-cyclopropene complex was studied (92). Photolysis of a tungsten(II) tetrafluoroaryl metallacycle 1 and perfluoro-2-butyne results in the formation of the kinetic rf -vinyl complex 2 in which the fluoride is trans to the inserted acetylene and cis to both carbonyl ligands. Upon heating 2 is converted to the thermodynamic rf -vinyl complex 3 in which the fluoride ligand is now cis to the inserted alkyne and trans to one CO and cis to the second CO ligand as shown in Scheme 1. 

The palladium(II)-catalyzed oxidation of allenes with chloride was studied by Hege-dus et al. [3], In this reaction the dimeric products 4 and 6 as shown in Scheme 17.4 were obtained. The (allene)palladium(II) complex formed can react with chloride ions in two different ways (Scheme 17.4) [4]. Attack at the terminal carbon gives a vinylpalladium intermediate 2 whereas attack at the middle carbon produces a 2-chloro(jt-allyl)palladium complex 3. The former complex is the kinetic intermediate (k2 > kj) and is in equilibrium with the (allene)palladium complex. The 2-chloro(jt-allyl)palladium complex is formed more slowly but is more stable and has been isolated [2]. The vinyl complex can undergo further reaction with excess allene to give a new (jt-allyl)palladium complex, which undergoes attack with chloride to give the observed dimer 6 [3]. The dichloride from attack on the 2-chloro-(jT-allyl)palladium complex 3 was not observed. 

It is worth noting that in most of the reactions involving allenes with an internal nucleophile, cr-vinyl complexes are formed but their further reaction usually lead to unwanted by-products. 

From the energetically preferred n-alkyne complex there is an alternative pathway involving the hydride ligand (Figure 5). The first step is an easy (AE = 6.6 kcal.mol 1) migratory insertion of the C=C triple bond into the cis Ru-H bond to yield a a-vinyl complex, A, 10.4 kcal.mol 1 below the it-alkyne complex. This 14-electron o-vinyl complex has also a saw-horse... 

The species shown in Schemes 8.1 and 8.2 do not contain vacant coordination sites suitable for binding weakly donating ligands such as alkenes. Even in Breslow s zwitterionic intermediate (Scheme 8.1) the nature of the metal-ethene interaction is unclear alkenes do not bind to the LUMO of 16-electron complexes CP2MCI2 (M = Ti, Zr, Hf) or their alkyl derivatives. The isolation by Eisch in 1985 of a cationic titanium vinyl complex [Cp2TiC(Ph)=C(Me)SiMe3], apparently formed by insertion of an alkyne into a putative [Cp2TiMe] intermediate [29], raised the... 

Addition of neutral nucleophiles to C affords the corresponding vinyl complexes, whereas anionic nucleophiles usually give carbene complexes. 

Coordination of the metal ion activates the carbon-carbon triple bond toward nucleophilic attack to yield a cr-vinyl complex (22), which is a characteristic pathway of metal-catalyzed additions to the acetylenic bond. Protolysis of 22 gives the end product. 

Catalytic systems to afford linear esters selectively are scant.306,309 A report in 1995 disclosed that palladium complexes based on l,l -bis(diphenylphosphine)fer-rocene showed excellent regioselectivity for the formation of linear a,p-unsaturated esters.309 The results with phenylacetylene are remarkable because this compound is known to exhibit a distinct preference for the formation of the branched products on palladium-catalyzed carboxylations. Mechanistic studies indicate that the alkoxycarbonylation of alkynes proceeds via the protonation of a Pd(0)-alkyne species to give a Pd-vinyl complex, followed by CO insertion and alcoholysis.310... 

Organomercurials react with Pt(PPh3)3 to form dialkyl platinum(II) complexes (equation 158).457,458 The method can be used for alkyl, aryl or vinyl complexes. 

The triple bond can be reduced with hydrazine to form the vinyl complex with a cis stereochemistry about the carbon-carbon double bond (equation 223).617 The five types ol reaction between platinum acetylide complexes and aprotic compounds A—B have beer summarized. These are (a) oxidative addition (A—B is I2, IBr, ICN, Mel etc.) (b) insertior (A—B is C2(CN)4) (c) addition across the triple bond to form vinyl complexes (A—B is CF3COCI, o-tetrachloroquinone, Br, NOC1) (d) insertion into the C—H bond (A—B is (CFs)2CO) and (e) formation of five-coordinate adducts.618... 

Many of the synthetic routes parallel those used to prepare alkene complexes c platinum(II). Replacement of chloride ion in PtClJ- by a water soluble alkyne is a frequentl used method (equation 266), 809 812 or the reaction can be assisted by the use of a silver salt t facilitate halide displacement (equation 267).813 With hexafluorobutyne-2 the five-coordinat adduct can be isolated before it converts into the vinyl complex (89 equation 268).814 Alkyne displace alkenes from platinum(ll) complexes. 

Alkynes coordinated to platinum(O) are susceptible to electrophilic attack. The reaction which has been most fully studied is the protonation of complexes Pt(alkyne)(PPh3)2 to give vinyl platinum(Il) complexes then alkenes. The reaction has been discussed in Section 52. The vinyl complexes formed undergo isomerization in the final step, since the cis vinyl complex yields some tracts-alkene. Carbene intermediates have been proposed in the pathway for this isomerization.848 Platinum(II) alkyne complexes can be converted into carbene complexes, and this reaction has been discussed in Section 52.4,6. This pattern of differential reactivity is apparent in the IR spectra of the two sets of complexes. For alkyne complexes of platinum(O) the C==C stretching frequency is lowered by some 450 cm-1 upon coordination, but with the platinum(II) analogs the difference is only in the region of 200 cm-1. 

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