Read e-book online Advances in Organometallic Chemistry, Vol. 17: Catalysis and PDF

By F.G.A. Stone, Robert West (Eds.)

ISBN-10: 0080580181

ISBN-13: 9780080580180

ISBN-10: 0120311178

ISBN-13: 9780120311170

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Extra info for Advances in Organometallic Chemistry, Vol. 17: Catalysis and Organic Syntheses

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2% highboiling materials. This system was stable for a 300 hour operating time, with no detectable loss of activity or selectivity. Polymers containing a benzyldiphenylphosphine complexing group are also effective. Capka et a l . (109) studied the catalyst formed from this type of organic substrate and RhCI,(C,H,), . 1-Hexene was hydroformylated with 40 atm of 3/4 H,/CO to produce 5696 n-heptaldehyde and 24% 2-methylhexaldehyde. Significant isomerization to internal olefins also occurred. Allurn and co-workers (110) studied several polymer types and focused on macroreticular, high surface area, cross-linked polystyrene.

Eng. , Prod. Res. Dev. 8,291 (1969). Copyright by the American Chemical Society. Thus, the rule of Keulemans (49), that a-quaternary carbon formyl compounds are not formed, was followed. The olefin isomerized to allow formyl attachment to a primary carbon atom. Addition of phosphine, which decreases isomerization. resulted in no reaction. B. Cyclic Olefins Differences in reactivity have been exhibited between acyclic and different types of cyclic olefins. Vinylcyclohexene in a cobalt hydroformylation at 120"-134°C and 475-720 atm pressure gave a 65% yield of a mixture of mono- and dialdehydes (66).

9 Reaction conditions: propylene, 20 g; ethanol, 80 g; ethyl orthoformate, 90 g; PHs,80 atm; Pco. 230 atm; temperature, 110°C. Hydroformy lation 21 pressure of 500 psi is significantly less than that employed in processes using CO,(CO)~[or HCo(CO),] as catalyst. However, it is recognized that phosphines are stronger a-donors and poorer r-acceptors than carbon monoxide. Thus, in Co,(CO),(PR,), or HCo(CO),PR, , the remaining carbon monoxide ligands are more strongly bound to the cobalt atom. because the metal tends to transfer the increased electron density back to the ligand.

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Advances in Organometallic Chemistry, Vol. 17: Catalysis and Organic Syntheses by F.G.A. Stone, Robert West (Eds.)

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