Concomitant Formation of N-Heterocyclic Carbene−Copper Complexes within a Supramolecular Network in the Self-Assembly of Imidazolium Dicarboxylate with Metal Ions

Chun, Jiseul; Jung, Il Gu; Kim, Hae Jin; Park, Soo‐Jin; Lah, Myoung Soo; Son, Seung Uk

doi:10.1021/ic900846s

Cited by 73 publications

(40 citation statements)

References 27 publications

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“…Basically, there are three synthetic methods by which azolium or NHC entities are incorporated into MOFs (see Scheme 1(b)): (1) azolium salts (without metalation) [125,126,129,144], (2) NHCs (metalation during the reaction) [147,149,150], or (3) premetalated NHCs [145]. Azolium salts without metalation have been incorporated into MOFs as monoimidazolium, bisimidazolium, or triazolium per ligand.…”

Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

“…Chun et al [150] used cadmium nitrate as a metal salt and an azolium salt-containing ligand, 1,3-bis(4-carboxy-2,6-diisopropylphenyl)imidazolium chloride, to design a one-dimensional MOF with two carboxylates coordinated to a single cadmium ion and two chlorides functioning as bridging ligands between the cadmium units, as can be observed in Fig. 22.…”

Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

“…Chun et al [149] worked in the same research direction by using cerium(III) nitrate with the same ligand as mentioned above [150] to construct three-dimensional supramolecular networks. Also, the imidazolium salts in the building blocks were intact during the self-assembly process and could be modified postsynthetically as shown in Fig.…”

Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

“…17) [129]. In addition, some other unusual zeolite-like geometries on the link component of the MOFs based on rigid linkers that have imidazolium integrated in the core of the ligand have been reported by Chun et al [149,150].…”

Section: Past Work On Azolium-containing Mofsmentioning

confidence: 95%

“…As far as the authors are aware, the first in situ generation of an NHC-metal complex within a supramolecular network was reported by Chun et al [150] in 2009. The two-dimensional MOF they assembled with copper(II) nitrate and 1,3-bis(4-carboxy-2,6-diisopropylphenyl)imidazolium chloride in dimethylformamide (DMF) under heating at a temperature of 110 • C contained two kinds of copper species, Cu(I) and Cu(II), within the structure.…”

Section: 1 -Methylenebis(3-(4-carboxyphenyl)-1h-imidazol-3-ium) Andmentioning

confidence: 99%

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Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

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Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

Section: Synthetic Methods Of Incorporating Azolium or Nhc Entities Imentioning

confidence: 99%

Section: Past Work On Azolium-containing Mofsmentioning

confidence: 95%

Section: 1 -Methylenebis(3-(4-carboxyphenyl)-1h-imidazol-3-ium) Andmentioning

confidence: 99%

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Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

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Carbenes Made Easy: Formation of Unsymmetrically Substituted N‐Heterocyclic Carbene Complexes of Palladium(II), Platinum(II) and Gold(I) from Coordinated Isonitriles and their Catalytic Activity

et al. 2010

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From palladium(II) or platinum(II) bis(isonitrile) complexes and from gold(I) isonitrile complexes, both easily available from simple precursors, the corresponding mono-N-heterocyclic carbene (NHC) complexes could be obtained selectively in good yields under very mild conditions. The reagents are simple b-chloroammonium salts in the presence of a weak base. Unsymmetric NHC complexes are accessible. Thus over only two steps from simple metal precursors a broad variety of NHC complexes is available, the method is ideal to quickly assemble catalyst libraries. The palladium complexes are active pre-catalysts in Suzuki cross-coupling even with the additional isonitrile ligand on palladium.

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Modular Synthesis of Functionalisable Alkoxy‐Tethered N‐Heterocyclic Carbene Ligands and an Active Catalyst for Buchwald–Hartwig Aminations

et al. 2014

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Modular syntheses of functionalised, alkoxy-tethered 1,3-bis(2,4,6-trimethylphenyl)imidazolium (IMes·H + ) and 1,3-bis(2,6-diisopropylphen-,6-diisopropylphenyl)imidazolium (IPrO R ·H + ) are reported. A reliable synthesis of the key starting material 4-amino-3,5-diisopropylphenol is also described. Etherification of hydroxydecorated ligand intermediates before formation of the imidazolium core and subsequent modification, or direct etherification of the versatile synthon IPrO H ·HCl, allowed access to various linker types including triethoxysilyl, primary amino and norbornenyl, which are not accessible by other methods. An IPrO R -palladium(II) complex was prepared, and its catalytic activity was evaluated in challenging Buchwald-Hartwig aminations of aryl chlorides. This precatalyst displayed excellent activity and selectivity under mild reaction conditions, achieving in some cases a 10-fold improvement in TOF relative to the IPr-based version. An unexpected activity profile was observed wherein sterically demanding anilines were coupled more easily than those lacking orthosubstitution. 461 FULL PAPERSModular Synthesis of Functionalisable Alkoxy-Tethered NHC cially available 4-amino-3,5-dimethylphenol (1a, Scheme 2) as starting material for the synthesis of oligomer [11c,d] or bulky alkyl-decorated [22] Grubbs-Hoveyda metathesis catalysts bearing alkoxy-modified SIMes analogues. Similar methodology can be envisioned for the formation of IPr analogues; however, to the best of our knowledge 4-amino-3,5-diisopropylphenol (1b, Scheme 2) has not been reported outside the patent literature, and the synthesis described is unattractive. [23] Therefore, an improved synthesis of this valuable intermediate was needed which employs readily available materials. As shown in Scheme 2, 2,6-diisopropylaniline (2) was oxidised [24] to the nitrobenzene 3 and subsequently partially reduced to the putative hydroxylamine 4 using methodology based on literature precedent. [25] The crude product was then directly treated with aqueous acid to effect a Bamberger rearrangement, [26] affording 1b in acceptable yield over two steps.The previous NHC syntheses employing 1a required protection of the aminophenol before a Mitsunobu-type etherification in one case, [11c] or direct etherification (in low yield) in the other. [22] We found that, under the proper reaction conditions, N,N'-bis-A C H T U N G T R E N N U N G (hydroxyaryl)diazabutadienes 5a/b (prepared from 1a/ b by condensation with a glyoxal equivalent) could be used directly for etherification to produce alkene-decorated 6a/b in excellent yield without the need for protection/deprotection steps (Scheme 3).Conversion of the functionalised diazabutadienes 6a/b to their corresponding imidazolium NHC precursors 7-9 was accomplished following two different routes (Scheme 3). The trifluoromethanesulfonate salts IXyO ene ·HOTf (7a) and IPrO ene ·HOTf (8a) were prepared using conditions reported by Glorius, [5a] employing in situ-generated pivaloylmethyl trifluoromethanesulfonate as a C ...

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Concomitant Formation of N-Heterocyclic Carbene−Copper Complexes within a Supramolecular Network in the Self-Assembly of Imidazolium Dicarboxylate with Metal Ions

Cited by 73 publications

References 27 publications

Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

Carbenes Made Easy: Formation of Unsymmetrically Substituted N‐Heterocyclic Carbene Complexes of Palladium(II), Platinum(II) and Gold(I) from Coordinated Isonitriles and their Catalytic Activity

Modular Synthesis of Functionalisable Alkoxy‐Tethered N‐Heterocyclic Carbene Ligands and an Active Catalyst for Buchwald–Hartwig Aminations

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