Dimerization of alkenes by palladium- and rhodium chlorides

Ketley, A. D.; Fisher, L. P.; Berlin, Alvin J.; Morgan, C. R.; Gorman, E. H.; Steadman, Thomas R.

doi:10.1021/ic50050a005

Cited by 58 publications

(11 citation statements)

References 2 publications

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“…Similar equilibria and cis complexes have been proposed in related systems (I, 27,28,48). The next step in the reaction pathway has been thought to be a two-carbon insertion reaction.…”

Section: Palladium Complexes 117supporting

confidence: 77%

See 1 more Smart Citation

Chemistry of Palladium Complexes

Schultz

Gross

1974

Advances in Chemistry

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The vinylation of acetic acid by higher olefins has been studied. Using the hexenes as model compounds, the struc tures of the products have been elucidated both for the vinylation products and for the higher boiling materials pro duced under certain conditions. The effect of several reac tion parameters on the course of the reaction has been studied. Both the ratio of vinylation products to higher boiling products and the distribution of isomers within the vinyl esters depend on the relative amount of acetate ion present. High levels of specific vinyl esters could be pro duced by the correct choice of olefin and reaction parame ters. With α-olefins, primary esters could be produced with greater than 75% specificity. As an alternate for the cur rently accepted vinylation mechanism, a new reaction pathway is proposed.Cince the first report of synthesizing vinyl acetate from ethylene (37), ^ a number of other reports on this reaction ( Reaction 1 ) have appeared (4,

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“…Similar equilibria and cis complexes have been proposed in related systems (I, 27,28,48). The next step in the reaction pathway has been thought to be a two-carbon insertion reaction.…”

Section: Palladium Complexes 117supporting

confidence: 77%

“…A one-carbon insertion reaction similar to that proposed above could also be used to account for the observed dimerization of ethylene and propylene by palladium(II) systems (28,56). A possible route for this reaction is given in Reaction 17.…”

Section: Xviia Xviibmentioning

confidence: 90%

Chemistry of Palladium Complexes

Schultz

Gross

1974

Advances in Chemistry

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“…We have reported previously that dihydridotetrakis(triphenylphosphine)ruthenium(II) (1) reacts with olefins such as ethylene and styrene to afford olefin-coordinated complexes, Ru(olefin)(PPh3)3, together with formation of the hydrogenated products of the olefins.55 When a large excess of ethyl methacrylate was allowed to react with 1 at room temperature, a Et(2b), z-Pr(2c), and n-Bu (2d) yellow complex with an apparent composition of Ru(ethyl methacrylate)(PPh3)3, precipitated out in a day with the concomitant formation of 1 mol equiv of ethyl isobutyrate, the hydrogenation product of ethyl methacrylate. Analyses of the complex by means of infrared and NMR spectra, elemental analyses, and chemical reactions, however, all suggest that this diamagnetic complex is hydrido(2-ethoxycarbonylpropenyl-C1,0)tris(triphenylphosphine)ruthenium(II) (2). This formulation is confirmed by an x-ray diffraction study of the «butoxy complex (vide infra).…”

Section: Resultsmentioning

confidence: 91%

Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-C1,O)tris(triphenylphosphine)ruthenium(II)

Komiya¹,

Ito²,

Cowie³

et al. 1976

J. Am. Chem. Soc.

100

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“…In the early days of homogeneous catalysis simple transition metal salts like RuCl 3 and RhCl 3 were reported to catalyse the dimerisation of ethylene under rather extreme conditions. [36,37] Alkylaluminium activators and donor ligands were, however, found to improve the activity. [38] For the catalyst system [Co(acac) 3 ]/AlEt 3 (acac acetylacetone) a selectivity for 1-butene of more than 99.5 % was reported.…”

Section: Introductionmentioning

confidence: 99%

Oligomerisation of Ethylene by Bis(imino)pyridyliron and -cobalt Complexes

et al. 2000

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A series of bis(imino)pyridyliron and -cobalt complexes [[2,6-(CR=NAr)2C5H3N]MX2] (R=H, Me; M=Fe, Co; X=Cl, Br) 8-16 containing imino-aryl rings (Ar) with at least one small ortho substituent, as well as Ar=biphenyl and Ar=naphthyl, has been synthesised. Crystallographic analyses of complexes 9 (Ar = 2,3-dimethylphenyl), 13 and 14 (Ar= biphenyl; X= Cl or Br, respectively) reveal a distorted trigonal-bipyramidal geometry in the solid state. These complexes, in combination with methyl aluminoxane (MAO), are active catalysts for the oligomerisation of ethylene, yielding >99% linear alpha-olefin mixtures that follow a Schulz-Flory distribution. Iron ketimine (R = Me) precatalysts give the highest activities and a greater alpha-value than their aldimine (R = H) analogues. Cobalt precatalysts follow a similar trend, though their activities are almost two orders of magnitude lower than those of the corresponding iron catalysts. Ethylene pressure studies on cobalt precatalyst 15 reveal a first-order dependence on ethylene for both the rate of propagation and the rate of chain transfer, and a pressure independence of the alpha value.

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Dimerization of alkenes by palladium- and rhodium chlorides

Cited by 58 publications

References 2 publications

Chemistry of Palladium Complexes

Chemistry of Palladium Complexes

Carbon-hydrogen bond activation by transition metal complexes. Oxidative addition of alkyl methacrylate to ruthenium. The structure of hydrido(2-n-butoxycarbonylpropenyl-C1,O)tris(triphenylphosphine)ruthenium(II)

Oligomerisation of Ethylene by Bis(imino)pyridyliron and -cobalt Complexes

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