Novel Hydroformylation catalysts

Slaugh, Lynn H.; Mullineaux, Richard D.

doi:10.1016/s0022-328x(00)82775-8

Cited by 226 publications

(138 citation statements)

References 12 publications

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“…Hydrogen transfer to the alkene is influenced by the steric demand of the ligand, leading to either Markovnikov or, preferentially, anti-Markovnikov addition. In the case of unmodified catalysis, the symmetry of the species should yield equal amounts of linear and branched aldehydes (1/b = 1), and addition of CO produces the alkyl species [RCH 2 CH 2 Co(CO) 3 L] (7). Alkyl migration to a coordinated CO ligand results in the acyl species [R′C(O)Co(CO) 3 L] (8) which is cleaved by hydrogen to form the aldehyde and regenerate the hydride 4.…”

Section: L] (4)mentioning

confidence: 99%

“…20 The data are in agreement with the literature, 20 and only new data are reported. A solution of P(OPh) 3 3 ) was added to this mixture and an immediate phase separation was observed. The light yellow organic phase was separated from the dark blue aqueous phase.…”

Section: Synthesis Of [Co 2 (Co) 6 {P(oph) 3 } 2 ] (2)mentioning

confidence: 99%

“…Hydroformylation today is the most important application of homogeneous catalysis on an industrial scale, 2 with worldwide production capacities about 6 million ton year −1 . The first generation of catalysts was based on unmodified [HCo(CO) 4 ], which required high reaction pressures to ensure the stability of the active catalyst and to avoid cobalt plating. In 1966, [3][4][5] Shell reported a system where the addition of a tertiary phosphine stabilised the catalyst to such an extent that reaction pressures below 100 bar were feasible.…”

Section: Introductionmentioning

confidence: 99%

“…The first generation of catalysts was based on unmodified [HCo(CO) 4 ], which required high reaction pressures to ensure the stability of the active catalyst and to avoid cobalt plating. In 1966, [3][4][5] Shell reported a system where the addition of a tertiary phosphine stabilised the catalyst to such an extent that reaction pressures below 100 bar were feasible. These modified systems were less reactive than the unmodified one and resulted in a decrease in reaction rates upon increasing the concentration of ligand.…”

Section: Introductionmentioning

confidence: 99%

“…7 This mechanism was later generalised and applied to ligand modified systems as well (Scheme 1), in which the catalyst precursor is the mono-substituted hydride, [HCo(CO) 3 …”

Section: Introductionmentioning

confidence: 99%

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Synthesis, crystal structure and hydroformylation activity of triphenylphosphite modified cobalt catalysts

Haumann¹,

Meijboom²,

Moss

et al. 2004

Dalton Trans.

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The dinuclear complex [Co 2 (CO) 6 {P(OPh) 3 } 2 ] (2) has been synthesised and was fully characterised. The solid state structure revealed a trans diaxial geometry, no bridging carbonyls, and Co-Co and Co-P bond lengths of 2.6722(4) and 2.1224(4) Å, respectively. Catalysed hydroformylation of 1-pentene with 2 was attempted at temperatures in the range 120 to 210 °C and pressures between 34 and 80 bar. High pressure spectroscopy (HP-IR and HP-NMR) was used to detect hydride intermediates. High pressure infrared (HP-IR) studies revealed the formation of [HCo(CO) 3 P(OPh) 3 ] (4) at ca. 110 °C, but at higher temperatures absorption bands corresponding to [HCo(CO) 4 ] (3) were observed. The hydride intermediate 4 has also been synthesised and characterised. Upon increased ligand concentration, HP-IR studies showed the formation of new carbonyl absorption bands due to a higher substituted cobalt carbonyl complex-[HCo(CO) 2 {P(OPh) 3 } 2 ] (5), which is believed to be catalytically less active. Complex 5 has been synthesised independently and was fully characterised. A low temperature crystal structural study of 5 revealed a trigonal bipyramidal structure with a trans H-Co-CO arrangement and two equatorial phosphite ligands, the Co-P bond lengths being 2.1093(8) and 2.1076(8) Å, respectively.

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Section: L] (4)mentioning

confidence: 99%

Section: Synthesis Of [Co 2 (Co) 6 {P(oph) 3 } 2 ] (2)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…7 This mechanism was later generalised and applied to ligand modified systems as well (Scheme 1), in which the catalyst precursor is the mono-substituted hydride, [HCo(CO) 3 …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis, crystal structure and hydroformylation activity of triphenylphosphite modified cobalt catalysts

Haumann¹,

Meijboom²,

Moss

et al. 2004

Dalton Trans.

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Sodium Tetracarbonylcobaltate

Kerr

2001

Encyclopedia of Reagents for Organic Synthesis

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Carbonylation Processes by Homogeneous CatalysisBased in part on the article Carbonylation Processes by Homogeneous Catalysis by George G. Stanley which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Parr

2005

Encyclopedia of Inorganic Chemistry

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This article reviews homogeneously catalyzed carbonylation reactions with particular emphasis on catalytic hydroformylation using cobalt, rhodium, platinum, and palladium complexes. The carbonylation of methanol based on rhodium and iridium complexes (Monsanto and Cativa ™ processes, respectively) is also discussed. Examples of the utility of carbonylation in the synthesis of complex molecules are given.

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Novel Hydroformylation catalysts

Cited by 226 publications

References 12 publications

Synthesis, crystal structure and hydroformylation activity of triphenylphosphite modified cobalt catalysts

Synthesis, crystal structure and hydroformylation activity of triphenylphosphite modified cobalt catalysts

Sodium Tetracarbonylcobaltate

Carbonylation Processes by Homogeneous CatalysisBased in part on the article Carbonylation Processes by Homogeneous Catalysis by George G. Stanley which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

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