Functionalized phosphine substituted cobalt carbonyls. Synthesis, characterization and catalytic activity in the hydroformylation of olefins

Rosi, Luca; Bini, Antonella; Frediani, Piero; Bianchi, Mario; Salvini, Antonella

doi:10.1016/1381-1169(96)00135-5

Cited by 20 publications

(16 citation statements)

References 8 publications

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“…Comparison of catalytic properties in the series Co2(CO)6[PR3] (R=CEP, Bu, (CH2)2CO2Me, (CH2)3OMe) in hexene-1 and propene hydroformylation revealed that complexes with CEP ligand demonstrated lower regioselectivity in relation to linear aldehydes (53% in contrast to 60-61% for other phosphines) and conversion level (26% versus 38-42%) which may be connected with the lowest solubility of CEP complexes in this series [140].…”

Section: Rhodium(iii) Complexes 167mentioning

confidence: 96%

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Odinets¹,

Vinogradova²,

Matveeva³

et al. 2005

COC

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Synthetic approaches to both linear and cyclic cyano-substituted phosphines (P~CN-phosphines) found an industrial application as catalyst precursors, pesticides, herbicides, flame retardants, precursors of aminophosphines etc., are reported. The main synthetic routes include reduction of P=O containing precursors, alkylation of silylphosphines and metal phosphides by halogenoalkyl(aryl)carbonitriles, phosphorylation of the latter ones, decomposition of phosphonium salts and hydrophosphination of cyano-substituted olefins proceeding under non-catalytical conditions and with use of metal complex catalysis. Merits and demerits of each approach are discussed. Phosphines bearing cyano function as an additional coordination site show diverse coordination behavior depending on the phosphine structure and nature of the metal. Four main types of complexes are observed, namely those with P-monodentate coordination, with N-monodentate coordination and complexes where bidentate coordination mode of P and N atoms is realized either at the single metal atom or of bridged type between two different metal atoms. Thus coordination behavior of such P~CN-ligands relative to transition and non-transition metals, structure features of the complexes obtained and their application in catalytic processes are discussed.

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Section: Rhodium(iii) Complexes 167mentioning

confidence: 96%

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Odinets¹,

Vinogradova²,

Matveeva³

et al. 2005

COC

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“…The use of 1 or 0 eq (eq = molar equivalent) of ligand was not investigated, since the use of 2 eq of a phosphine ligand in HF reactions resulted in a higher selectivity for the aldehyde than 1 eq of phosphine ligand. [26,46] The use of 5 eq of P(n-Bu) 3 in HAM experiments resulted in a lower conversion and similar selectivity for the N-alkylated amine compared to the use of 2 eq of P(n-Bu) 3 ( Table 2). Reactions without ligand were not Figure 5.…”

Section: Hydroaminomethylation Of 1-octene and Pyrrolidinementioning

confidence: 99%

The Hydrogenation Problem in Cobalt‐based Catalytic Hydroaminomethylation

et al. 2020

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The hydroaminomethylation (HAM) reaction converts alkenes into N-alkylated amines and has been well studied for rhodiumand ruthenium-based catalytic systems. Cobalt-based catalytic systems are able to perform the essential hydroformylation reaction, but are also known to form very active hydrogenation catalysts, therefore we examined such a system for its potential use in the HAM reaction. Thus, we have quantum-chemically explored the hydrogenation activity of [HCo(CO) 3 ] in model reactions with ethene, methyleneamine, formaldehyde, and vinylamine using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. Our computations reveal essentially identical overall barriers for the catalytic hydrogenation of ethene, formaldehyde, and vinylamine. This strongly suggests that a cobalt-based catalytic system will lack hydrogenation selectivity in experimental HAM reactions. Our HAM experiments with a cobalt-based catalytic system (consisting of Co 2 (CO) 8 as cobalt source and P(n-Bu) 3 as ligand) resulted in the formation of the desired N-alkylated amine. However, significant amounts of hydrogenated starting material as well as alcohol (hydrogenated aldehyde) were always formed. The use of cobalt-based catalysts in the HAM reaction to selectively form N-alkylated amines seems therefore not feasible. This confirms our computational prediction and highlights the usefulness of state-of-the-art DFT computations for guiding future experiments.

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“…The higher alkene feed (C [10][11][12][13][14] for the production of detergent alcohols is either a product from the wax-cracker (terminal and internal alkenes) or the byproduct of the ethene oligomerisation process (internal alkenes). In the near future a feed from high-temperature Fischer-Tropsch may be added to this.…”

Section: Cobalt Catalysed Processes For Higher Alkenesmentioning

confidence: 99%

“…Ligand effects in a series of tertiary phosphines L=P(C 3 H 6 OCH 3 ) 3 , PBu 3 , P(C 2 H 4 CO 2 CH 3 ) 3 , and P(C 2 H 4 CN) 3 has been studied using the complexes Co 2 (CO) 6 (L) 2 as the catalyst precursor [12]. For a 1 : 1 ligand to cobalt ratio the results were the same for all ligands and the percentage of linear products amounted to 60% (40 bar H 2 , 5 bar CO, 150 °C).…”

Section: Phosphine Derivativesmentioning

confidence: 99%

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Cobalt Catalysed Hydroformylation

2004

Homogeneous Catalysis

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Functionalized phosphine substituted cobalt carbonyls. Synthesis, characterization and catalytic activity in the hydroformylation of olefins

Cited by 20 publications

References 8 publications

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

Synthesis and Coordination Chemistry of Cyano-Substituted Phosphines

The Hydrogenation Problem in Cobalt‐based Catalytic Hydroaminomethylation

Cobalt Catalysed Hydroformylation

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