Synthesis, characterization and structural study of a phosphonium salt containing the [Pd 2 Br 6 ] 2− ion and its application as a novel, efficient and renewable heterogeneous catalyst for amination of aryl halides and the Stille cross-coupling reaction

Naghipour, Ali; Ghorbani‐Choghamarani, Arash; Heidarizadi, Fateme; Notash, Behrouz

doi:10.1016/j.poly.2015.11.051

Cited by 13 publications

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References 42 publications

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“…The reaction of 2′ with 4 equiv of PdBr 2 in CH 3 CN yields a brown precipitate, tentatively assigned as [( 2 )Pd 2 Br 2 ][Pd 2 Br 6 ] (Scheme ). This assignment is based on the reported reaction of PDI Ph [ N , N ′-(2,6-pyridinediyldiethylidyne)bis-benzenamine] and PdCl 2 to produce [(PDI Ph )PdCl][PdCl 3 ] − and crystallographic evidence that shows that PdBr 3 – exists as the Pd 2 Br 6 2– dimer. − [( 2 )Pd 2 Br 2 ][Pd 2 Br 6 ] was not characterized due to poor solubility but rather was converted to [( 2 )Pd 2 Br 2 ][BAr F 4 ] 2 by anion exchange using NaBAr F 4 [Ar F = 3,5-(CF 3 ) 2 -Ph] in 63% overall yield from 2′ and PdBr 2 . The solid-state structure of [( 2 )Pd 2 Br 2 ][BAr F 4 ] 2 is shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

Reinhart

Jordan

2019

Inorg. Chem.

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We describe the template-free synthesis of the bis(pyridine-dienamine) proligand [4,5-(m-xylylenediamine)NH–C(CH)(9-butyl-octahydroacridine)]2 (2′), a variant of Burrows’s macrocyclic bis(pyridine-diimine) (bis-PDI) ligand [2,6-(m-xylylenediamine)NC(py)]2 (A), using octahydroacridine as the ligand backbone. The octahydroacridine backbone favors macrocyclization by constraining the PDI units in the (s-cis)2 conformation. The template-free synthesis of 2′ enables facile access to a wide array of bis-PDI and bis(pyridine-dienamido) (bis-PDE) metal complexes. Five-coordinate binuclear bis-PDI (2)M2Cl4 complexes {2 = [4,5-(m-xylylenediamine)NC(9-butyl-octahydroacridine)]2; M = Zn, Co, or Fe} and a four-coordinate bis-PDI [(2)Pd2Br2][B(3,5-(CF3)2-Ph)4]2 complex were synthesized and characterized. (2)Zn2Cl4 undergoes macrocyclic ring inversion on the nuclear magnetic resonance (NMR) time scale with a free energy barrier ΔG ⧧ of 15.5(3) kcal/mol at 295 K. In contrast, (2)Fe2Cl4 and (2)Co2Cl4 undergo slow ring inversion on the NMR chemical shift time scale at 295 K. The amine elimination reaction of 2′ with Zr(NMe2)4 yields the bis-PDE complex (2′-4H)Zr2(NMe2)4, which was alkylated with AlMe3 and Al(CH2SiMe3)3 to generate (2′-4H)Zr2Me4 and (2′-4H)Zr2(CH2SiMe3)2(NMe2)2, respectively.

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Section: Resultsmentioning

confidence: 99%

Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

Reinhart

Jordan

2019

Inorg. Chem.

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“…(°C): Liquid 1 a: X=I, 10 h, 90 % TON [c] /TOF [d] (h À 1 ) 21/1.2 1 b: X=Br, 14 h, 63 % TON/TOF(h À 1 ) 15/1.1 1 c: X=Cl, 18 h, 0 % TON/TOF(h À 1 ) 0 m.p. (°C): 142-144 (142-145 [27] ) 1 d: X=I, 10 h, 94 % TON/TOF(h À 1 ) 22/2.2 1 e: X=Br, 18 h, 71 % TON/TOF(h À 1 ) 17/1.0 1 f: X=Cl, 18 h, 60 % TON/TOF(h À 1 ) 14/0.8 m.p. (°C): 141-143 (143 [59] ) 1 g: X=Br, 15 h, 94 % TON/TOF(h À 1 ) 22/1.5 1 h: X=Cl, 18 h, 88 % TON/TOF(h À 1 ) 21/1.2 2 d 2 e 2 f m.p.…”

Section: Experimental Instrumentsunclassified

“…(°C): 141-143 (143 [59] ) 1 g: X=Br, 15 h, 94 % TON/TOF(h À 1 ) 22/1.5 1 h: X=Cl, 18 h, 88 % TON/TOF(h À 1 ) 21/1.2 2 d 2 e 2 f m.p. (°C): 136-139 (136-138 [27] ) 1 i: X=Br, 18 h, 90 % TON/TOF(h À 1 ) 21/1.2 1 j: X=Cl, 18 h, 55 % TON/TOF(h À 1 ) 13/0.7 m.p. (°C): 180-183 (182-185 [60] ) 1 k: X=Br, 12 h, 93 % TON/TOF(h À 1 ) 22/1.8 1 l: X=Cl, 18 h, 70 % TON/TOF(h À 1 ) 16/0.9 m.p.…”

Section: Experimental Instrumentsunclassified

A New Bis‐(NHC)‐P(II) Complex Supported on Magnetic Mesoporous Silica: An Efficient Pd(II) Catalyst for the Selective Buchwald‐Hartwig Monoarylation of Ammonia

et al. 2023

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We report the synthesis and identification of a new bis(NHC)‐Pd(II) catalyst supported on magnetic SBA‐15 (Fe3O4@SBA‐15). The surface of magnetic SBA‐15 was subsequently treated with (3‐aminopropyl) triethoxysilane (APTES), cyanuric chloride (CC), imidazole, and 2‐bromopyridine. The modified magnetic mesoporous material was then further treated with separately prepared trans‐[Pd(Cl)2(SMe2)2] complex to give Fe3O4@SBA‐AP‐CC‐bis(NHC)‐Pd(II) as a supported bis(NHC)‐Pd(II) complex. The catalyst was fully characterized by common spectroscopic methods. X‐ray photoelectron spectroscopy (XPS) revealed that some imine nitrogens interact with palladium atoms. The supported Pd(II) complex catalyzed the direct monoarylation of ammonia with iodo‐, bromo‐, and chloroarenes, selectively. The effects of reaction components and parameters were investigated to establish the optimal reaction conditions. The catalyst was separated by a magnet, washed, and applied in the subsequent run. It exhibited noticeable stability and reused over seven catalytic cycles with negligible deactivation. A small Pd leaching (1.04 %) was observed in the first run.

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“…To solve this problem, several noble strategies involving heterogeneous and improvised homogeneous catalysts have been developed for recycling and reusing Stille catalysts, including the use of Pd complexes supported by recombinant peptide fusion nanoparticles [ 16 ], magnetic nanoparticles [ 17 ], stainless steel mesh-GO (graphene oxide) nanoparticles [ 18 ], polymer [ 19 , 20 , 21 ], silica [ 22 ], porous metal-organic framework (MOF) [ 23 ], functionalized nanoporous silica [ 24 , 25 ], bulky ligands [ 26 ] and metal nanoparticles [ 27 , 28 ]. Additionally, a few reaction solvent options, including alcohols [ 29 , 30 ], water [ 31 , 32 , 33 ], and ionic liquid [ 34 , 35 ] were also studied to ensure that successful recovery occurred. Similarly, several recoverable Suzuki-Miyaura catalysts, including the use of Pd complexes supported by agar [ 36 ], polymer [ 37 ], aminophosphine supported on Al 2 O 3 [ 38 ], perovskite-based [ 39 ], and magnetically recoverable ones [ 40 , 41 ] were used.…”

Section: Introductionmentioning

confidence: 99%

Recoverable Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions under Thermomorphic Mode: Stille and Suzuki-Miyaura Reactions

et al. 2021

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The reaction of [PdCl2(CH3CN)2] and bis-4,4’-(RfCH2OCH2)-2,2’-bpy (1a–d), where Rf = n-C11F23 (a), n-C10F21 (b), n-C9F19 (c) and n-C8F17 (d), respectively, in the presence of dichloromethane (CH2Cl2) resulted in the synthesis of Pd complex, [PdCl2[4,4’-bis-(RfCH2OCH2)-2,2’-bpy] (2a–d). The Pd-catalyzed Stille arylations of vinyl tributyltin with aryl halides were selected to demonstrate the feasibility of recycling usage with 2a as the catalyst using NMP (N-methyl-2-pyrrolidone) as the solvent at 120–150 °C. Additionally, recycling and electronic effect studies of 2a–c were also carried out for Suzuki-Miyaura reaction of phenylboronic acid derivatives, 4-X-C6H4-B(OH)2, (X = H or Ph) with aryl halide, 4-Y-C6H4-Z, (Y = CN, H or OCH3; Z = I or Br) in dimethylformamide (DMF) at 135–150 °C. At the end of each cycle, the product mixtures were cooled to lower temperature (e.g., −10 °C), and then catalysts were recovered by decantation with Pd leaching less than 1%. The products were quantified by gas chromatography/mass spectrometry (GC/MS) analysis or by the isolated yield. The complex 2a-catalyzed Stille reaction of aryl iodides with vinyl tributyltin have good recycling results for a total of 8 times, with a high yield within short period of time (1–3 h). Similarly, 2a–c-catalyzed Suzuki-Miyaura reactions also have good recycling results. The electronic effect studies from substituents in both Stille and Suzuki-Miyaura coupling reactions showed that electron withdrawing groups speed up the reaction rate. To our knowledge, this is the first example of recoverable fluorous long-chained Pd-catalyzed Stille reactions under the thermomorphic mode.

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Synthesis, characterization and structural study of a phosphonium salt containing the [Pd 2 Br 6 ] 2− ion and its application as a novel, efficient and renewable heterogeneous catalyst for amination of aryl halides and the Stille cross-coupling reaction

Cited by 13 publications

References 42 publications

Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

Template-Free Synthesis of a Macrocyclic Bis(pyridine-dienamine) Proligand and Metal Complexes of Its Bis(pyridine-diimine) and Bis(pyridine-dienamido) Forms

A New Bis‐(NHC)‐P(II) Complex Supported on Magnetic Mesoporous Silica: An Efficient Pd(II) Catalyst for the Selective Buchwald‐Hartwig Monoarylation of Ammonia

Recoverable Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions under Thermomorphic Mode: Stille and Suzuki-Miyaura Reactions

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