Nickel(<scp>ii</scp>) complexes containing tridentate ONC<sup>i</sup> ligands (i = abnormal N-heterocyclic carbene donors) and their catalytic application in Suzuki–Miyaura coupling reaction

Lee, Jhen‐Yi; Hsieh, Meng-Jun; Ho, Tsai-En; Wu, Bo-Hsin; Lee, Hon Man

doi:10.1039/d1dt04114b

Cited by 5 publications

(3 citation statements)

References 63 publications

(82 reference statements)

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“…The replacement of precious metals with earth-abundant and less-expensive metals in well-established catalytic processes is one of the main challenges of modern chemistry. In this context, Lee and co-workers have designed a new family of nickel-NHC complexes as efficient homogeneous precatalysts for Suzuki–Miyaura coupling reactions . The target complexes were synthesized by reacting Ni(OAc) 2 ·4H 2 O with an excess of the tridentate phenoxy-amidate-aNHC (aNHC = abnormal NHC) proligand in neat pyridine with potassium carbonate as the weak base at 130 °C (Scheme ).…”

Section: Well-defined Metal-n-heterocyclic Carbene Precatalystsmentioning

confidence: 99%

“…In this context, Lee and co-workers have designed a new family of nickel-NHC complexes as efficient homogeneous precatalysts for Suzuki− Miyaura coupling reactions. 118 The target complexes were synthesized by reacting Ni(OAc) 2 •4H 2 O with an excess of the tridentate phenoxy-amidate-aNHC (aNHC = abnormal NHC) proligand in neat pyridine with potassium carbonate as the weak base at 130 °C (Scheme 63). The chemical structure of these nickel derivatives is the result of an unexpected degradation pathway that involves the coordination of an imidazole moiety instead of the pyridine at the remaining coordination site of the metal center.…”

Section: Carbene Precatalystsmentioning

confidence: 99%

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Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

Scattolin,

Logvinov,

Tzouras

et al. 2023

Organometallics

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N-heterocyclic carbene (NHC) ligands have evolved from being simple lab curiosities to tertiary phosphine mimics to finally take center stage as unique supporting ligands in organometallic chemistry, homogeneous catalysis, and more recently in medicinal chemistry and materials science applications. Some of these aspects are presented here from a perspective of researchers that have been fascinated by the area for quite some time.

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Section: Well-defined Metal-n-heterocyclic Carbene Precatalystsmentioning

confidence: 99%

Section: Carbene Precatalystsmentioning

confidence: 99%

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

Scattolin,

Logvinov,

Tzouras

et al. 2023

Organometallics

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“…Crabtree and co-workers described an aNHC-metal complex in 2001, but the stable unmasked aNHC was reported in 2009 by Bertrand et al Tolman electronic parameters and quantum chemical calculations predicted a stronger electron donating ability of aNHCs versus the corresponding nNHCs . The exceptional donating ability of the aNHC ligands has made them crucial in the design and synthesis of multidentate ligands, in particular, pincer architectures where NHCs serve as terminal donors . Also, the use of aNHCs has emerged as a new strategy to synthesize high valence metal complexes .…”

Section: Introductionmentioning

confidence: 99%

A Cationic Pt(II) Dinitrogen Adduct: Synthesis and Characterization of a CCC-aNHC Pincer Pt Complex with Abnormal N-Heterocyclic Carbene Donor Arms

Fosu,

Le,

Abdulraheem

et al. 2024

Organometallics

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In contrast to the reported CCC-NHC pincer ligands that contain normal N-heterocyclic carbenes (NHC), herein we report an imidazole-based abnormal NHC (aNHC) pincer ligand, CCC-aNHC. The CCC-aNHC pincer Pt complex with two aNHC donors was synthesized via the in situ metalation and transmetalation methodology. The 1,3-phenylene(bis-2phenyl-3-butyl imidazolium) diiodide salt was reacted with Zr(NMe 2 ) 4 to generate a CCC-aNHC pincer zirconium complex in situ. It was transmetalated to Pt using [Pt(COD)Cl 2 ]. Electrospray ionization of the Pt pincer complex [( Bu C a-i C a-i C Bu )-PtI] in acetonitrile generated an intense peak at m/z = 696.2375, which was assigned to the dinitrogen adduct [M−I+N 2 ] + of the cationic CCC-aNHC pincer Pt(II) complex [( Bu C a-i C a-i C Bu )Pt− N 2 ] + , representing a rare example of the platinum dinitrogen organometallic complex. The super electron-donating ability of the pincer ligands with abnormal NHC enabled the cationic CCC-aNHC pincer Pt(II) complex to selectively bind N 2 over MeCN in a first-order analysis. A collision-induced dissociation (CID) study was conducted on the N 2 and MeCN adducts, suggesting that more energy was required to dissociate N 2 than MeCN. A computational study suggested that the N 2 adduct was kinetically stable in the gas phase whereas the MeCN adduct was thermodynamically preferred. The computational results reconciled the mass spectral data experiment with an attempt to isolate the N 2 adduct. DFT computation suggested that N 2 dissociation is more challenging due to higher energy transition states, and there is a competitive pathway of N 2 tumbling within the coordination sphere of the Pt. This tumbling path is not available from the MeCN ligand due to ligand structural differences.

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Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

Chernenko,

Baydikova,

Kutyrev

et al. 2024

ChemCatChem

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Aryl chlorides, due to their affordability and accessibility, are preferred reagents in Pd‐catalyzed arylation reactions. However, the reactivity of aryl chlorides is often reduced compared to aryl bromides and iodides due to the significantly higher barriers of the oxidative addition stage. This research introduces a novel design for NHC ligands, which notably enhances the efficiency of Pd/NHC catalytic systems in reactions where oxidative addition of aryl chloride is the rate‐limiting step. This design leverages a synergy between specific steric characteristics and the anionic nature of the newly fashioned 1,2,4‐triazol‐5‐ylidene ligands. These ligands, inspired by Nitron‐type designs, can be ionized under basic conditions due to their NH‐acidic aryl(alkyl)amino groups. Detailed experimental and DFT studies revealed that the deprotonation of these NHCs promotes electron donation to the metal center, promoting the oxidative addition of aryl chloride. The specially optimized ATPr ligand, featuring 2,6‐diisopropylphenyl groups, displayed remarkable catalytic efficacy in the Suzuki‐Miyaura reaction and improved outcomes in ketone α‐arylation and Buchwald‐Hartwig reactions with unactivated aryl chlorides. The insights and strategies established in this study provide rational considerations for further advancements in NHC designs and their applications in metal‐catalyzed reactions.

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Nickel(ii) complexes containing tridentate ONCⁱ ligands (i = abnormal N-heterocyclic carbene donors) and their catalytic application in Suzuki–Miyaura coupling reaction

Abstract: A Ni(ii) complex with tridentate phenoxy–amidate–aNHC donors was synthesized, which was efficient in Suzuki–Miyaura coupling with additional IMes·HCl.

Cited by 5 publications

References 63 publications

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

A Cationic Pt(II) Dinitrogen Adduct: Synthesis and Characterization of a CCC-aNHC Pincer Pt Complex with Abnormal N-Heterocyclic Carbene Donor Arms

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

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Nickel(ii) complexes containing tridentate ONCi ligands (i = abnormal N-heterocyclic carbene donors) and their catalytic application in Suzuki–Miyaura coupling reaction

Abstract: A Ni(ii) complex with tridentate phenoxy–amidate–aNHC donors was synthesized, which was efficient in Suzuki–Miyaura coupling with additional IMes·HCl.

Cited by 5 publications

References 63 publications

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

Advances in the Synthesis and Applications of N-Heterocyclic Carbene Metal Complexes with a Focus on the Weak Base Route

A Cationic Pt(II) Dinitrogen Adduct: Synthesis and Characterization of a CCC-aNHC Pincer Pt Complex with Abnormal N-Heterocyclic Carbene Donor Arms

Base‐Ionizable Anionic NHC Ligands in Pd‐catalyzed Reactions of Aryl Chlorides

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Nickel(ii) complexes containing tridentate ONCⁱ ligands (i = abnormal N-heterocyclic carbene donors) and their catalytic application in Suzuki–Miyaura coupling reaction