Study of carbon monoxide insertion into the carbon—cobalt bond

Nagy-Magos, Zsuzsa; Bor, G.; Markó, László

doi:10.1016/s0022-328x(00)92657-3

Cited by 61 publications

(19 citation statements)

References 6 publications

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“…Taking into account the peculiar behavior under oxo conditions of double bonds conjugated with phenyl rings (14), it might be assumed that: electronic effects produce predominately the disubstituted benzylcobalt complex CH, C6H5-C-Co-; and that steric and electronic considerations indicate I C2H, a labile configuration of the tertiary asymmetric carbon atom. Since the formation of the acyl compounds is not favored (15) in benzylcobalt complexes, hydrogenolysis and hence hydrogénation is favored over car bon monoxide insertion followed by hydroformylation when starting with tertiary alkylcobalt complex. Furthermore the configurational lability of the intermediate yields a racemic hydrogénation product.…”

Section: Methodsmentioning

confidence: 99%

“…H2,CO,cat* * R-CH-CH=CH2 > R-CH-CH2-CH2-CHO I partial | R' conversion R r + R-CH-CH=CH2 % % figuration 2-pheny lpropanal 6 24 1.9 S 2-phenylpropanaldiethylacetal b 2-pheny lpropanal 6 15 15.2 R 2-phenylpropanaldiethylacetal b 2-pheny lpropanal 6 20 0.3 R S-phenylbutanaF 11 2.5 S S-phenylbutanaldiethylacetal 7 5 0.6 R 3-phenylpentanal 9 2 The main reaction product is cumene (90-95%). 0 The main reaction product is 2-phenylbutane (94%).…”

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confidence: 99%

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Asymmetric Hydroformylation. Hydroformylation of Olefins in the Presence of Chiral Rhodium and Cobalt Catalysts

Pino

Consiglio

Botteghi

et al. 1974

Advances in Chemistry

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Optical yields up to 17% and 25%, respectively, have been reached in the styrene hydroformylation in the presence of cobalt or rhodium catalysts using N-alkylsalicylaldimine or phosphines as asymmetric ligands. Furthermore the hydro formylation of aliphatic and internal olefins have been achieved using rhodium catalysts in the presence of opti cally active phosphines. With the same catalysts, cis -butene surprisingly undergoes asymmetric hydroformulation with optical yields up to 27%. On the basis of the results obtained for cis-butene and the asymmetric induction phenomena in dichlor(olefin)(amine)platinum(II) com plexes, a simple model is proposed for the catalytic complex. The correlation among the prevailing chirality obtained in the asymmetric hydroformylation of vinyl, vinylidene, and internal olefins is discussed.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Asymmetric Hydroformylation. Hydroformylation of Olefins in the Presence of Chiral Rhodium and Cobalt Catalysts

Pino

Consiglio

Botteghi

et al. 1974

Advances in Chemistry

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“…This may explain why during the induction period a well detectable amount of Co 2 (CO) 8 is formed, while probably only a small amount of RH is formed. When the concentration of HCo(CO) 4 in solution will substantially decrease, the second reaction will start to successfully compete with the reaction of the polynuclear alkyl with HCo(CO) 4 , and the polynuclear acyl cobalt complex will start to form [24][25][26][27][28].…”

Section: Proposed New Alternative Mechanismmentioning

confidence: 99%

Re-evaluation of the mechanism of the stoichiometric hydroformylation of olefins with cobalt carbonyls as catalysts

Tannenbaum¹,

Bor²

2004

Journal of Molecular Catalysis A: Chemical

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“…Mark& eta/. (25) have shown that the benzylcobalt complex C61 IsCtq2Co(CO)3IP(C6H5)3], which is a relatively stable crystalline compound, reacts in solution with 13CO (20 °C, 1 atm) according to…”

Section: Hco(co)3lmentioning

confidence: 99%

Reactions of carbon monoxide with transition metal-carbon bonds

Henrici‐Olivé¹,

Olivé²

1976

Transition Met Chem

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SummaryInsertions of carbon monoxide into transition metal-carbon bonds are among the most selective methods for the catalytic introduction of oxygen into organic compounds. A variety of processes are known today and most of them are of great industrial importance. Depending on the nature of the organic substrate, the catalyst and additional reaction components products range from aldehydes, alcohols, and acids to esters, anhydrides, acid chlorides, amides etc. An attempt is made here to show that all these reactions proceed by similar mechanisms. General AspectsAmong the most selective methods to catalytically introduce oxygen into organic substrates are those involving carbon monoxide. In most cases, transition metal carbonyl complexes have been identified, or are assumed, as catalysts [e.g. HCo(CO)a, HRh(CO)(PR3) 3, Ni(CO)4].In general, these reactions involve the insertion of CO into a metal-carbon bond with subsequent decomposition of the acyl-metal complex by reaction with a nucleophilic substance having an active hydrogen (H-Y). The metal-carbon bond is formed by insertion of an olefin (or acetylene) into a metalhydride bond, or by oxidative addition of an alkyl halide (RX) to a coordmatively unsaturated metal species. These two routes are summarized here as Schemes 1 and 2, respectively. Scheme 2 includes substrates such as alcohols, ethers, esters, etc. In general, halide ions are required as cocatalysts: presumably RX is formed in situ from the substrate (RZ) and HX. The reaction products range from aldehydes, alcohols, acids, esters, to anhydrides, acid chlorides, amides, etc., depending on the nature of the substrate and the component HY (56).

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Study of carbon monoxide insertion into the carbon—cobalt bond

Cited by 61 publications

References 6 publications

Asymmetric Hydroformylation. Hydroformylation of Olefins in the Presence of Chiral Rhodium and Cobalt Catalysts

Asymmetric Hydroformylation. Hydroformylation of Olefins in the Presence of Chiral Rhodium and Cobalt Catalysts

Re-evaluation of the mechanism of the stoichiometric hydroformylation of olefins with cobalt carbonyls as catalysts

Reactions of carbon monoxide with transition metal-carbon bonds

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