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- W2359784339 abstract "Complex [Rh(κ2-P,P-dppe)2]acac ([1a]acac, dppe: 1,2-bis(diphenylphosphino)ethane) showed to be a highly efficient precatalyst for the hydroformylation of 1-hexene with formaldehyde under relatively mild reaction conditions (353–403 K) in 1,4-dioxane as the solvent; the corresponding C7 aldehydes were obtained in linear to branched ratios (l/b) close to 2. A kinetic study for this reaction lead to the experimentally determined rate law: ri = {K1k2/(1 + K1[CH2O])}[Rh][C6H12][CH2O] [K1 = (1.47 ± 0.04) M−1 and k2 = (0.47 ± 0.01) M−1s−1 at 373 K). The experimental activation parameters for the overall reaction were also calculated [Ea = (20.1 ± 0.9) kcal mol−1, ΔH≠ = (19.5 ± 0.9) kcal mol−1, ΔS≠ = (−9.3 ± 0.5) cal K−1 mol−1 and ΔG≠ = (22 ± 2) kcal mol−1]. The kinetic study together with results on coordination chemistry performed with 1a and with the BF4 salt of its iridium analogue, [Ir(κ2-P,P-dppe)2]BF4 ([1b]BF4), as well as theoretical DFT-calculations allowed us to propose a mechanism for this reaction. The catalytic cycle involves the reversible oxidative addition of formaldehyde to 1a to yield [Rh(H)(CHO)(κ2-P,P-dppe)2]+, followed by the insertion of the olefin into the Rh-H bond to generate [Rh(alkyl)(CHO)(κ2-P,P-dppe)2]+, which is considered as the rds of the process [Ea2 = (23.9 ± 0.8) kcalmol−1]; the cycle is completed by the reductive elimination of the aldehydes to regenerate 1a and restart the cycle." @default.
- W2359784339 created "2016-06-24" @default.
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- W2359784339 date "2016-09-01" @default.
- W2359784339 modified "2023-10-14" @default.
- W2359784339 title "Kinetics and mechanisms of homogeneous catalytic reactions. Part 14. Hydroformylation of 1-hexene with formaldehyde catalyzed by a cationic bis(diphosphine)rhodium complex" @default.
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- W2359784339 doi "https://doi.org/10.1016/j.molcata.2016.05.014" @default.
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