On the Mechanism of the Oxo Reaction

Orchin, Milton; Rupilius, Wolfgang

doi:10.1080/01614947208078692

Cited by 141 publications

(55 citation statements)

References 54 publications

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“…The analyses of the catalysts after reaction, see Table 3, revealed that during the reaction some soluble cobalt species had formed. This observation is, in fact, in accordance with the literature [26,27,44,45]. Homogeneous and heterogeneous activity were difficult to distinguish, due to the batch to batch variations in catalytic performance.…”

Section: Co/sosupporting

confidence: 80%

Hydroformylation of 1-hexene on RhC and CoSiO2 catalysts

Kainulainen¹,

Niemelä²,

Krause³

1997

Journal of Molecular Catalysis A: Chemical

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The effect of the support for rhodium on activated carbon, and the effect of precursor for cobalt on silica, were studied in the liquid phase hydroformylation of 1-hexene. At best the activities of the heterogeneous catalysts were similar to their homogeneous counterparts. The activity of the Rh/C catalysts correlated with the support; the larger the pores the better the mass transfer, and the higher the activity. In the case of Co/SiO,, the effect of precursor on the activity of the catalysts was diverse, and the activities remained lower than that of the homogeneous cobalt carbonyl. Some metal was, however, dissolved from the supports, and consequently the activity was mainly due to the dissolved catalytic species rather than the heterogeneous catalyst. The dissolution of the metal from the support was due to both synthesis gas mediated formation of soluble active species, and reaction product effectuated dissolution. Yet, the heterogeneous functionality of the active carbon support was revealed by the formation of C,, acetals, which were only formed on a support with acidic character and large enough pores. The acidic character of the active carbon supports was also shown by the formation of C,, condensation products, which were only formed in traces for homogeneous rhodium.

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Section: Co/sosupporting

confidence: 80%

Hydroformylation of 1-hexene on RhC and CoSiO2 catalysts

Kainulainen¹,

Niemelä²,

Krause³

1997

Journal of Molecular Catalysis A: Chemical

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“…After our discovery of H 2 complexes in 1983, it was surprising to come across a review article by Orchin [25] published in 1972 on the mechanism of the oxo reaction which contained the precise bonding picture (figure 5) for g 2 -H 2 coordination that we now know to be true. Orchin even stated that the bonding involves backdonation to r* entirely analogous to that in metal-olefin p-bonding.…”

Section: Introductionmentioning

confidence: 94%

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

Kubas

2005

Catal Lett

109

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“…Indeed, the formation of HCo(CO) 4 from Co 2 (CO) 8 is widely believed to involve electron deficient compounds such as HCo(CO) 3 or Co 2 (CO) 7 [6][7][8][9][10]. Similarly to the stoichiometric hydroformylation, both the formation and the decomposition of HCo(CO) 4 are strongly dependent on CO concentration, as suggested by earlier work of Ungváry and Markó [11].…”

Section: Introductionmentioning

confidence: 84%