Hydroformylating Terminal Olefins

Tucci, Edmond R.

doi:10.1021/i360036a010

Cited by 64 publications

(36 citation statements)

References 8 publications

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“…It is therefore suggested that coordination of amine to rhodium increases the hydridic character of the Rh-H bond, much the same as is postulated in cobalt-tributylphosphine complexation (20). The differing effect of amine on rhodium (promoter) and on cobalt (inhibitor) is attributed to the more hydridic nature of a Rh-H bond as compared with the very protonic HCo(CO)4.…”

Section: Discussionmentioning

confidence: 74%

Hydroformylation with Rhodium-Amine Complexes

Jurewicz

Rollmann

Whitehurst

1974

Advances in Chemistry

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Under mild conditions, hydroformylation of olefins with rhodium carbonyl complexes selectively produces aldehydes.A one-step synthesis of oxo alcohols is possible using monomeric or polymeric amines, such as dimethylbenzylamine or anion exchange resin analog to hydrogenate the aldehyde. The rate of aldehyde hydrogenation passes through a maximum as amine basicity and concentration increase. IR data of the reaction reveal that anionic rhodium carbonyl clusters, normally absent, are formed on addition of amine. Aldehyde hydrogenation is attributed to enhanced hydridic character of a Rh-H intermediate via amine coordination to rhodium.Hydroformvlation of olefins to aldehydes over cobalt carbonyl catalysts A -1 * is the first step in the industrial synthesis of oxo alcohols (1, 2). Reaction conditions require temperatures above 150 °C and pressures up to 3000 psig. Subsequent aldehyde hydrogénation occurs over supported cobalt or molybdenum disulfide catalysts.Addition of modifying ligands such as tributyl phosphine affords a one-step, cobalt-catalyzed synthesis of alcohols (at lower pressure), but accompanying olefin hydrogénation reduces yields (3). With amine ligands, the effects are varied. Accelerated hydroformylation rates are possible with weak bases such as pyridine, but stronger bases ( piperidine or triethylamine, for example) retard or completely inhibit the reaction (4,5).In comparison with their cobalt analogs, rhodium carbonyls are significantly more active catalysts (6). As with cobalt, aldehyde is the 240

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Section: Discussionmentioning

confidence: 74%

Hydroformylation with Rhodium-Amine Complexes

Jurewicz

Rollmann

Whitehurst

1974

Advances in Chemistry

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“…A more plausible explanation is that the minor catalyst functions as a hydrogen-transfer catalyst for the major catalyst, M(CO)5(PBu3). Earlier studies of the organophosphine-complexed cobalt carbonyl catalyst suggested that this system possesses good hydrogenation activity (Slaugh and Mullineaux, 1968;Tucci, 1968Tucci, , 1970Kniese et al, 1969;Piacenti et al, 1970). Therefore, it is suggested that the HCo ( (5) In eq 3, minute amounts of dicobalt octacarbonyl react with PBu3 to form the dimeric complex which, in eq 4, is hydrogenated under oxo conditions to form the hydrocarbonyl complex.…”

Section: Resultsmentioning

confidence: 99%

“…Metal carbonyls of chromium (Cr), molybdenum (Mo), and tungsten (W) undergo mono-or disubstitution (Magee et al, 1961) While even further displacement of CO from the disubstituted complex is possible, it was not pursued in this work. The metal carbonyls are available from Pressure Chemical Co.; the trialkylphosphine, PBu3, is available from M&T Chemicals, Inc. Other types of organophosphines similar to those used in pure cobalt carbonyl systems (Tucci, 1969) were evaluated in this study, but discussions will be restricted to the PBu3 ligand. Except for a few exploratory hydroformylation runs using M-(CO),(PBU~)~ complexes, this investigation focused on the monosubstituted complex.…”

Section: Methodsmentioning

confidence: 99%

Binary oxo catalysts using chromium, molybdenum, or tungsten

Tucci¹

1985

Ind. Eng. Chem. Prod. Res. Dev.

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Hydroformylation catalysis of olefins was extended to include group 6 metal carbonyls of chromium, molybdenum, and tungsten. Hydroformylation activity and selectivity for pure M(CO)e catalysts were both low, whereas organophosphine complexes of the type M(CO),(PR,) exhibited good selectivity but still showed low catalytic activity. By the introduction of trace amounts of a second metal carbonyl such as cobalt, a binary metal catalyst system could be "custom tailored" to yield excellent catalytic activity and good selectivity. Catalytic activity was lower than a pure cobalt carbonyl-trialkylphosphine catalyst used in high concentration, and linear product formation was not as high for the binary catalyst systems. An unexpected synergistic effect was observed in these binary metal systems which contained a "major" catalyst M(CO),(PBu,) and a "minor" catalyst HCo(CO),PBu3. The active catalytic species exhibited the most desirable features of each individual metal catalyst. Binary catalysts of Cr/Co, Mo/Co, and W/Co all performed equally effectively as oxo catalysts when hydroformylating terminal or internal straight chain olefins. Mononuclear complexes of the type M(CO)5(FBu3) showed exceptionally high thermal stabilii. Parametric studies were performed to determine optimum operating conditions for these unique catalyst systems. In trod uctionCommercial oxo processes which once used pure cobalt carbonyl catalysts exclusively now include organophosphine-complexed cobalt or rhodium carbonyl catalysts. While cobalt and rhodium catalysts are excellent for hydroformylating olefins to alcohols, both are based on strategic metals which must be imported from abroad. Any major long-term disruption in availability of these metals could lead to serious consequences for oxo alcohol producers. Several years ago cobalt availability was a cause for concern, although major shortages did not materialize. Rhodium availability has not posed any serious threats to date. However, since the producer's price for this metal has approached $800 per troy ounce since its commercial use in low-pressure oxonation, high rhodium recovery is essential to achieve high process efficiency. To maximize catalyst efficiency, i.e., the cost of catalyst per pound of product produced, a rhodium-triphenylphosphine catalyst is best applicable in propene oxonation rather than higher olefin oxonation since the product/catalyst separation step facilitates high rhodium recovery.Several major concerns prompted the investigation of metal systems other than cobalt or rhodium as potential hydroformylation catalysts. To lessen the chance of strategic metal shortages, the oxo catalyst had to be based principally on metals produced in the U.S. The producer's price for such metals had to be more in line with base metals rather than precious metals. To favor process economics, the oxo catalyst had to possess exceptionally high thermal stability to facilitate an efficient direct separation of high molecular weight oxo products from the catalyst. Finally, catalyst activity...

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“…The sdonor and p-acceptor character of EPh 3 ligand will be the governing factor for the dissociation of M-EPh 3 bond. Tucci [16] has also reported that the rate of olefin hydroformylation reaction is strongly dependent on the ligand basicity (i.e., the ligand of low basic character supports a faster rate of hydroformylation reaction). As discussed earlier, sbasicity is lower for AsPh 3 than for PPh 3 and SbPh 3 .…”

Section: Discussionmentioning

confidence: 99%