Ir-catalyzed tandem hydroformylation-transfer hydrogenation of olefins with (trans-/cis-)formic acid as hydrogen source in presence of 1,10-phenanthroline

Liu, Lei; Gao, Han; Yang, Shuqing; Chen, Xiao-Chao; Lu, Yong; Xia, Fei

doi:10.1016/j.jcat.2020.03.008

Cited by 14 publications

(7 citation statements)

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“…Rh and Ir were selected to be the coordinated unsaturated sites in M–Cu–BTC as these two metals are the most active centers in homogeneous catalysts. 50,51 In the present study, the DFT study has been performed on the propene hydroformylation reaction on M–Cu–BTC (M = Rh, Ir). The mechanism of the propene hydroformylation reaction catalyzed by Rh–Cu–BTC and Ir–Cu–BTC was proposed.…”

Section: Introductionmentioning

confidence: 99%

The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study

et al. 2022

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Section: Introductionmentioning

confidence: 99%

The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study

et al. 2022

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“…When PhBr was applied in place of PhI, 56% conversion of PhBr was obtained (entry 15 vs 1) along with 86% selectivity to the α-ketoamide. Due to the C–Br bond being stronger than C–I, the sluggish oxidative addition of PhBr to Pd catalyst A (Scheme ), which was the rate-determining step for this carbonylation, dramatically limited the transformation rate of PhBr.…”

Section: Resultsmentioning

confidence: 99%

“…In order to deeply understand the reaction pathway towards the amino dicarbonylation or aminocarbonylation over different Pd catalysts, the evolving reaction processes of PhI with Et 2 NH in CO atmosphere (0.5 MPa) were further monitored in situ by FT-IR spectroscopy 40 (Figure 5). As shown in Figure 5A, over the PdCl 2 (MeCN) 2 -Xantphos catalytic system, the absorption at 1598 cm −1 appeared gradually when the temperature increased from 30 up to 100 °C, which was attributed to the characteristic peak of carbonyl group in N,Ndiethylbenzamide as the aminocarbonylated product (see Figure S3a with the authentic sample as reference).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides

et al. 2021

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The amino dicarbonylation of aryl halides affording α-ketoamides with Pd catalysts is highly dependent on the stereoelectronic properties of the involved ligands. Ionic diphosphine ligand L4 can serve as precursor of a hemilabile P,C (phosphine, carbene)-hybrid ligand to form a stable Pd(II)complex, Pd-L4. In contrast, analogues L1−L3 with a similar 1-(thiophen-3-yl)-benzimidazolyl skeleton behave as typical (mono/ di)phosphines. The catalytic system resulting from the complexation of PdCl 2 (MeCN) 2 and L4 exhibits good catalytic performance in terms of aryl iodides conversion (81−95%) and αketoamide selectivity (80−91%), as well as the available recyclability in the RTIL of [Bpy]BF 4 . The in situ FT-IR analysis reveals that the PdCl 2 (MeCN) 2 −L4 catalytic system favors the amino dicarbonylation toward α-ketoamides according to the proposed mechanism of cycle I, which involves two independent COinsertion steps.

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“…In parallel, together with the search for new organic ligands, other metals, such as ruthenium, iridium, iron, platinum, or palladium, have been also investigated to tune the intrinsic catalytic properties of the metal. [24][25][26][27][28][29][30][31][32][33] Regarding ruthenium based catalysts, it has been reported that in general mononuclear carbonyl ruthenium complexes exhibit higher activity and selectivity than polynuclear complexes so that their activity and selectivity can be tuned by a suitable ligand system. [34][35][36][37] This is the case of Ru 3 (CO) 12 which when combined with an imidazoyl-substituted monophosphine and other heterocycle-derived phosphine ligands can provide good activities and tunable selectivity towards the aldehyde and/or alcohol.…”

Section: Introductionmentioning

confidence: 99%

Chitosan‐Silica as a Cheap Carrier and Green Soft Ligand for Improved Ru‐catalyzed Hydroformylation

et al. 2022

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Dodecacarbonyltriruthenium Ru3(CO)12 has been immobilized onto a biopolymer (chitosan) supported on SiO2 (Ch@SiO2) to give Ru−Ch@SiO2. Ch@SiO2 behaves as a soft, recoverable and bulky ligand allowing the stabilization of released Ru active species and preventing its irreversible reduction to Ru0. Under these conditions very high activity (TOF= 1086 h−1; TON=2749) and regioselectivity (n:iso=92 : 8) are obtained, surpassing that of the homogeneous Ru3(CO)12 counterpart. Spectroscopic studies have shown that Ru3(CO)12 transforms into a mononuclear Run+ (n=2,3) di o try carbonyl species by interacting with the amido/amino groups of the biopolymer, being released into the reaction media whilst stabilized by the chitosan functional groups. The herein 0.5 Ru‐Ch@SiO2 catalyst can operate be operated under a semi‐continuous mode for at least 14 h without deactivation, representing providing a starting point in the search for a green catalyst with definitive industrial application in hydroformylations. In particular in the search for a heterogeneous catalyst away from the use of phosphines and their known drawbacks (i. e. tedious synthesis, facile oxidation of phosphor center, ..) as well as expensive Rh as active site.

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Ir-catalyzed tandem hydroformylation-transfer hydrogenation of olefins with (trans-/cis-)formic acid as hydrogen source in presence of 1,10-phenanthroline

Cited by 14 publications

References 50 publications

The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study

The mechanism of MOF as a heterogeneous catalyst for propene hydroformylation: a DFT study

Pd-Catalyst Containing a Hemilabile P,C-Hybrid Ligand in Amino Dicarbonylation of Aryl Halides for Synthesis of α-Ketoamides

Chitosan‐Silica as a Cheap Carrier and Green Soft Ligand for Improved Ru‐catalyzed Hydroformylation

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