Tunable Rh(I) Fischer carbene complexes for application in the hydroformylation of 1-octene

Mashabane, Tshegofatso Lydia; Ramollo, G. Kabelo; Kleinhans, George; Doncker, Stephen de; Siangwata, Shepherd; Fernandes, Manuel A.; Lemmerer, Andreas; Smith, Gregory S.; Bezuidenhout, Daniela Ina

doi:10.1016/j.jorganchem.2020.121341

Cited by 4 publications

(3 citation statements)

References 57 publications

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“…The chemical shifts of the carbene 13 C resonance of δ( 13 C carbene ) = 196.0/195.9 (3a/3b), 214.0/213.0 (2a/2b) and 216.7/215.8 ppm (4a/4b) correlate with the Tolman electronic parameter 89 (TEP) of the carbene ligands with Fc < 4-DMA < 2furyl. 90,91 The 2-furyl substituent stabilizes the carbene p π orbital best, while the ferrocenyl substituent is less involved in inductive or π-resonance stabilization of the p π orbital. The pendant NMe 2 group has only a minor influence on δ( 13 C carbene ).…”

Section: ■ Introductionmentioning

confidence: 99%

Redox Activation of Acyclic (Aryl)(amino)carbene Gold(I) Complexes

Schrick,

Ramollo,

Hirschbiegel

et al. 2024

Organometallics

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Activation of halido gold(I) precatalysts Au(L)X to a cationic species [Au(L)] + with a vacant coordination site for substrate binding typically requires abstraction of the halide X − . The Fischer-type carbene gold(I) precatalysts 2−4 feature redoxactive dimethylanilinyl, 2-furyl, and ferrocenyl substituents without (2a−4a) and with (2b−4b), a dangling dimethylamino substituent. After single-electron oxidation, 2−4 catalyze the cyclization of N(2-propyn-1-yl)benzamide to 2-phenyl-5-vinylidene-2-oxazoline without the presence of a halide scavenger. While all dimethylanilinyl and 2-furyl substituted precatalysts likely form catalytically active nanoparticles after oxidation, the ferrocenyl substituted gold(I) complexes 4a and 4b operate in a homogeneous fashion. The dimethylamino substituted ferrocenyl precatalyst 4b is the most active one. The formation of the catalytically active molecular species after oxidation was probed by stopped-flow experiments, quantitative EPR spectroscopy, and quantum chemical calculations to arrive at a consistent mechanistic picture that involves one-electron oxidation of the ferrocene, valence isomerization to a gold(II) species and anion coordination to the gold(II) center. This oxidation/isomerization/coordination activation mechanism is fundamentally different from the typical activation of gold(I) precatalysts by halide abstraction and opens new avenues in gold catalysis beyond gold(I) and gold(III) catalyses.

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Section: ■ Introductionmentioning

confidence: 99%

Redox Activation of Acyclic (Aryl)(amino)carbene Gold(I) Complexes

Schrick,

Ramollo,

Hirschbiegel

et al. 2024

Organometallics

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“…Compared with Co‐based catalysts, Rh‐based catalysts have attracted much attention due to their excellent catalytic activity and mild reaction conditions. Usually, basic research and industrial hydroformylation processes are carried out under homogeneous Rh‐based catalysts, thus various Rh compounds modified by ligands have been well developed 19–29 . The TONs of propylene hydroformylation catalyzed by Rh can be as high as 14,508 30 …”

Section: Introductionmentioning

confidence: 99%

“…Usually, basic research and industrial hydroformylation processes are carried out under homogeneous Rh-based catalysts, thus various Rh compounds modified by ligands have been well developed. [19][20][21][22][23][24][25][26][27][28][29] The TONs of propylene hydroformylation catalyzed by Rh can be as high as 14,508. 30 It is shocking that though Rh and Ir belong to the same family in the periodic table of elements, their catalytic reactivities in the hydroformylation process follow the order Rh>>Ir.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous coordinated polymers with single‐metal‐site iridium for efficient catalysis in propylene hydroformylation

Yao,

Xiong,

Sun

et al. 2024

AIChE Journal

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Heterogeneous single‐metal‐site catalysts (SMSCs) have received increasing attention due to their outstanding stability and recyclability. In this work, a novel Ir‐based SMSC was successfully constructed through the coordination polymerization between zirconium and triphenylphosphine derivatives with carboxyl functional groups for efficient propylene hydroformylation with CO. The Ir‐based SMSC reported here can achieve a turnover number of over 20,000 (being 7.3 times higher than the most effective Ir‐base catalyst to date) with 99% selectivity and 56% yield for aldehyde. Besides, it represents the first example with a higher selectivity of isobutyraldehyde than n‐butyraldehyde (i.e., n/i = 0.62) among the reported Ir‐based catalysts. The Ir‐based SMSC can be easily reused for at least 10 cycles without losing its reactivity, whereas the homogeneous monomer catalyst quickly loses its reactivity after the second cycle. Furthermore, the catalytic mechanism of Ir‐based SMSC is proposed based on reaction explorations and in situ co‐adsorption tests by the method of diffuse reflectance infrared Fourier transform spectroscopy, which has also been revealed by theoretical calculations. This work provides a novel insight into the design of SMSCs with great potential for application in the hydroformylation field.

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Alkoxycarbonylation of Unsaturated Substrates of Plant Origin in the Presence of Palladium Catalysts as a Route to Synthesize Ester Products

Sevostyanova,

Batashev

2023

Catal. Ind.

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Tunable Rh(I) Fischer carbene complexes for application in the hydroformylation of 1-octene

Cited by 4 publications

References 57 publications

Redox Activation of Acyclic (Aryl)(amino)carbene Gold(I) Complexes

Redox Activation of Acyclic (Aryl)(amino)carbene Gold(I) Complexes

Mesoporous coordinated polymers with single‐metal‐site iridium for efficient catalysis in propylene hydroformylation

Alkoxycarbonylation of Unsaturated Substrates of Plant Origin in the Presence of Palladium Catalysts as a Route to Synthesize Ester Products

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