A Bis (BICAAC) Palladium(II) Complex: Synthesis and Implementation as Catalyst in Heck-Mizoroki and Suzuki-Miyaura Cross Coupling Reactions

Chakrabortty, Soumyadeep; Kaur, Mandeep; Adhikari, Manu; Manar, Krishna K.; Singh, Sanjay

doi:10.1021/acs.inorgchem.0c03614

Cited by 20 publications

(9 citation statements)

References 70 publications

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“…The modification of the ring allowed the synthesis of bicyclic carbenes (BICAAC‐6) with favorable electronic and steric properties (Scheme 2). [28] Although some transition metal complexes of BICAAC ligands have recently been reported, their ruthenium derivatives are rare [38–42] …”

Section: Methodsmentioning

confidence: 99%

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

et al. 2022

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One of the most exciting scientific challenges today is the catalytic degradation of non-biodegradable polymers into value-added chemical feedstocks. The mild pyrolysis of polyolefins, including high-density polyethylene (HDPE), results in pyrolysis oils containing long-chain olefins as major products. In this paper, novel bicyclic (alkyl)(amino)carbene ruthenium (BICAACÀ Ru) temperature-activated latent olefin metathesis catalysts, which can be used for catalytic decomposition of long-chain olefins to propylene are reported. These thermally stable catalysts show significantly higher selectivity to propylene at a reaction temperature of 75 °C compared to second generation Hoveyda-Grubbs or CAACÀ Ru catalysts under ethenolysis conditions. The conversion of long-chain olefins (e.g., 1-octadecene or methyl oleate) to propylene via isomerization-metathesis is performed by using a (RuHCl)(CO)(PPh 3 ) 3 isomerization co-catalyst. The reactions can be carried out at a BICAACÀ Ru catalyst loading as low as 1 ppm at elevated reaction temperature (75 °C). The observed turnover number and turnover frequency are as high as 55 000 and 10 000 mol propylene mol catalyst À 1 h À 1 , respectively.

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Section: Methodsmentioning

confidence: 99%

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

et al. 2022

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“…44c In 2021, Singh et al reported a (BICAAC) 2 PdCl 2 complex that showed better catalytic performance than other (NHC) 2 Pd catalysts for the Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions (Scheme 16). 45 Only a 0.5 mol% catalyst loading was sufficient for these reactions, whereas a 1-3 mol% catalyst loading was needed for other (NHC) 2 Pd catalysts.…”

Section: Bicaacmentioning

confidence: 99%

Ambiphilic singlet carbenes: Electron donors and acceptors

Kim

Lee

2022

Bulletin Korean Chem Soc

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The isolation of cyclic(alkyl)(amino)carbenes (CAACs) and N,N′‐diamidocarbenes (DACs) has opened up new avenues in the field of carbene chemistry due to their unique properties. CAACs are strong σ‐donors and π‐acceptors, whereas DACs are extremely strong π‐acceptors. The ambiphilicity of carbenes can facilitate new applications such as small molecule activation and catalysis. Since the isolation of CAACs and DACs, several new ambiphilic carbenes have been synthesized, thereby advancing the development of carbene chemistry. This review summarizes the most relevant findings on ambiphilic carbene chemistry until 2022.

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“…[9] Encouraged with the favourable ligand properties of BICAACs, we became interested to further harness the potential of metal-Me BICAAC complexes. Recently, we have reported on the catalytic activity of ( Me BICAAC) 2 PdCl 2 complex for Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions, [10] the reactivity of Me BICAAC with different hydroboranes [11] and synthesis of two coordinated Cu(I) and Au(I) complexes supported by Me BICAAC. [12] In the present report, we have synthesized Me BICAAC supported nickel complexes [( Me BICAAC) 2 NiX 2 ] (X = Cl (1), Br (2) and I (3)).…”

Section: Introductionmentioning

confidence: 99%

Well‐Defined Ni(0) and Ni(II) Complexes of Bicyclic (Alkyl)(Amino)Carbene (^MeBICAAC): Catalytic Activity and Mechanistic Insights in Negishi Cross‐Coupling Reaction

Thakur

Kaur

Manar

et al. 2022

Chemistry A European J

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Negishi cross‐coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well‐established library of Pd complexes, the C−C cross‐coupling of this particular approach is largely primitive with nickel‐complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl (1), Br (2), and I (3)) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1–3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] (4). Complexes 1–4 have been characterized by spectroscopic techniques and their solid‐state structures were also confirmed by X‐ray crystallography. Furthermore, complexes 1–4 have been applied in a direct and convenient method to catalyze the Negishi cross‐coupling reaction of various aryl halides with 2,6‐difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all‐pristine complexes, 1 exhibit high catalytic potential to afford value‐added C−C coupled products without the use of any additive. The UV‐vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta‐coordinated Ni(III)‐aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4.

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A Bis (BICAAC) Palladium(II) Complex: Synthesis and Implementation as Catalyst in Heck-Mizoroki and Suzuki-Miyaura Cross Coupling Reactions

Cited by 20 publications

References 70 publications

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

Ambiphilic singlet carbenes: Electron donors and acceptors

Well‐Defined Ni(0) and Ni(II) Complexes of Bicyclic (Alkyl)(Amino)Carbene (^MeBICAAC): Catalytic Activity and Mechanistic Insights in Negishi Cross‐Coupling Reaction

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A Bis (BICAAC) Palladium(II) Complex: Synthesis and Implementation as Catalyst in Heck-Mizoroki and Suzuki-Miyaura Cross Coupling Reactions

Cited by 20 publications

References 70 publications

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

Catalytic Decomposition of Long‐Chain Olefins to Propylene via Isomerization‐Metathesis Using Latent Bicyclic (Alkyl)(Amino)Carbene‐Ruthenium Olefin Metathesis Catalysts

Ambiphilic singlet carbenes: Electron donors and acceptors

Well‐Defined Ni(0) and Ni(II) Complexes of Bicyclic (Alkyl)(Amino)Carbene (MeBICAAC): Catalytic Activity and Mechanistic Insights in Negishi Cross‐Coupling Reaction

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Well‐Defined Ni(0) and Ni(II) Complexes of Bicyclic (Alkyl)(Amino)Carbene (^MeBICAAC): Catalytic Activity and Mechanistic Insights in Negishi Cross‐Coupling Reaction