The Influence of Hydrogen and Carbon Monoxide Partial Pressures on the Rate of the Hydroformylation Reaction

Natta, G.; Ercoli, R.; Castellano, S.; Barbieri, Filippo

doi:10.1021/ja01644a071

Cited by 61 publications

(25 citation statements)

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“…The inhibiting effect of the CO partial pressure was investigated by kinetic studies. 55 More than two decades later Wermer et al identied the complex HCo(CO) 3 with matrix infrared techniques. 56 It was proved that the hydrogenation of Co 2 (CO) 8 follows an associative pathway affording 2 molecules of HCo(CO) 4 and the reaction takes place via a radical pathway involving cCo(CO) 4 …”

Section: Generation Of the Active Catalystmentioning

confidence: 99%

Computational aspects of hydroformylation

Kégl

2015

RSC Adv.

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The influence of transition metal complexes as catalysts upon the activity and selectivity of hydroformylation reactions has been extensively investigated during the last decades. Nowadays computational chemistry is an indispensable tool for elucidation of reaction mechanisms and for understanding the various aspects which govern the outcome of catalytic reactions. This review attempts to survey the recent literature concerning computational studies on hydroformylation and theoretical coordination chemistry results related to hydroformylation.

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Section: Generation Of the Active Catalystmentioning

confidence: 99%

Computational aspects of hydroformylation

Kégl

2015

RSC Adv.

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“…I t was therefore necessary to study the kinetics of the reaction in order to ascertain if the 0x0 reaction of the glycals inight be controlled. Kinetic studies of the hydroformylation of cyclohexene (which appeared to be relevant to our research) a t various partial pressures of carbon monoxide and hydrogen under otherwise standard ex~erimental conditions had shown that the rate of the reaction was found to increase with an increase in the hydrogen pressure and to decrease n-ith an increase in the carbon monoxide pressure (6). In marked contrast, a kinetic study of the hydroforinylation of 3,4,6-tri-0-acetyl-D -~~u c~I (shown in Fig.…”

Section: Anhydro-3-deoxy-aldehydo-d-lyxo(and -D-xylo)-hexoses (I and mentioning

confidence: 88%

“…with benzene-methanol (95:5) as developer; n.m.r. (obtained in deuterated chloroform): 6 9.04-8.0 (equal to three aromatic protons), 6 7.85 (doublet, J = 9 c.p.s., equal to one hydrogen), and 6 For personal use only.…”

Section: Characterization Of Fraction a (45-di-0-acetyl-d6-mentioning

confidence: 99%

Hydroformylation of glycals

Rosenthal¹,

Abson²,

Field³

et al. 1967

Can. J. Chem.

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Hydroformylation of 3,4-di-0-acetyl-~-xylal gave 4,5-di-0-acetyl-2,6-anhydro-3-deoxyaldehyde-D-lyxo-hexose (I) and 4,5-di-0-acetyl-2,6-a1~hydro-3-deoxy-uldehydo-~-xylo-hexose iII). llethyl sulfoxide oxidation of 2,3-di-0-acet~~1-1,5-anhydro-4-deoxy-~-u~ubino-hexitol (111) and of 2,3-di-0-acetyl-l,5-anhl-dro-L-xylo-hex (IV) yielded compoullds I and 11, respectively.Reaction of 3,4,6-tri-0-acetyl-D-glucal with carbon inonoxide and hydrogen under carefully controlled conditions yielded 4,5,7-tri-0-acetyl-2,6-anhydro-3-deoxy-uldehydo-~-~unno-heptose (VII) and 4 , . 5 , 7 -t r i -0 -a c e t y l -2 , 6 -a n h y d r o -3 -d e o x~c o -h e p t o s e (VIII) in a 707; yield. Compound V I I was readily separated from the mixture of aldoses and alditols by column chromatography. Alternatively, aldoses VII and VIII were separated via their P,4-dinitrophenylhydrazones. The co~lversio~l of aldoses \;I1 and VIII into their diethyl dithioacetal derivatives is also described.The fortnyl group located in an equatorial orientation was found t o be reduced a t a faster rate than its axial counterpart.

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“…There is a growing amount of scientific knowledge on the formation and degradation reactions of the cluster carbonyls, however, mainly in terms of preparative routes. In contrast to the dramatic increase of efforts on this field, only a few studies are known which treat in a quantitative way the reversible reactions of type (1) or (2) with the aim of obtaining thermodynamical data for them. Mx(CO)y + a Co n Mx/n(CO){a+y}/n (1) Mx(CO)y + b H2 fl H2b,flMx/fl(CO){y.w}/fl + W CO (2) Besides the p se importance of the knowledge of the reaction enthalpies and entropies for such processes the direct determination of these thermodynamic parameters via measurements of the temperature variation of the equilibrium constants, represents a complementary source of thermochemical data, which adds to the direct calorimetric results.…”

Section: Introductionmentioning

confidence: 99%

“…1. 543 Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 7/6/15 12:43 PM 544 G.BOR (2) With the method of quantitative equilibrium measurements we can obtain the enthalpies of formation even for compounds which cannot be prepared in pure form. We present the corresponding values obtained in this way for Rh2(CO) 8 On this last mentioned equilibrium another study has been published meanwhile by Alemdarolu et al [4].…”

Section: Introductionmentioning

confidence: 99%

Metal carbonyl clusters: thermodynamics of their formation and stability. Some novel results on cobalt, rhodium, ruthenium, and mixed clusters

Bor¹

1986

Pure and Applied Chemistry

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A series of reversible cluster formation and degradation reactions with neutral metal carbonyls and carbonyl hydrides was studied by high-pressure IR-spectroscopy, under CO and/or H2 pressure, in alkane solutions. Fundamental reversible reactions were analyzed for cobalt, rhodium, ruthenium, and mixed Co-Fe, Co-Ru and Co-Rh carbonyl systems. Log K vs l/T equations, their graphical illustrations and thermodynamic parameters are given for the homometallic Co, Rh and Ru systems.In the combined system of Co and Ru carbonyls and hydridocarbonyls proper conditions were found where mixed hydridocarbonyl clusters are obtained in stable equilibria with the homonuclear compounds. Of the COx(HRu)4_x(CO)12 species the one with x=3 is strongly favored thermodynamically. -In the mixed Co-Fe system no thermodynamically stable compound could be found: HCo3Fe(CO)1 decomposes irreversibly, under CO as well as H2 or N, to homometallic species.Of particular interest is the coordinatively unsaturated mixed species CoRh(CO)7, which represents a key link between the homo-and hetero-metallic equilibria of these metals.The connection of our data with thermochemical results from other laboratories, and their application to bond enthapy calculations is presented.

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The Influence of Hydrogen and Carbon Monoxide Partial Pressures on the Rate of the Hydroformylation Reaction

Cited by 61 publications

References 1 publication

Computational aspects of hydroformylation

Computational aspects of hydroformylation

Hydroformylation of glycals

Metal carbonyl clusters: thermodynamics of their formation and stability. Some novel results on cobalt, rhodium, ruthenium, and mixed clusters

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