Bis(diphenylphosphinyl)-functionalized dipyrido-annulated NHC towards copper(<scp>i</scp>) and silver(<scp>i</scp>)

Zhang, Sihan; Shang, Rong; Nakamoto, Masaaki; Yamamoto, Yohsuke; Adachi, Yoshinori; Ohshita, Joji

doi:10.1039/c9dt02435b

Cited by 8 publications

(8 citation statements)

References 37 publications

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“…and Kunz et al − Both theoretical and experimental studies have shown that its aromatic dipyrido moieties contribute to empty p orbitals of the carbene carbon, resulting in a higher π-donating ability in comparison to Arduengo-type NHCs . Previously, we have successfully introduced thio, phosphinyl, − and aryl substituents to the dpa NHC backbone. The aryl-substituted dpa Ar2 NHCs were in situ generated by deprotonation of the respective imidazolium salt and characterized by complexation to a gold(I) center (Scheme ).…”

Section: Resultsmentioning

confidence: 98%

Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N-Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C–H Bond Activation

et al. 2021

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Meridional tridentate N-heterocyclic carbene (NHC)-based pincer ligands contribute to a substantial growth in modern organometallic chemistry in both homogeneous catalysis and luminescence materials. Among all NHC-based pincer ligands, the dianionic LX 2 -type CCC-pincer ones constitute the smallest subcategory owing to their limited ligand frameworks suitable for complexation. This work reports a one-pot, high-yield synthesis of a homoleptic anionic all-carbon bis-pincer iridium(III) complex (4) directly from a bis(aryl)-substituted dipyrido-annulated (dpa Ar2 ) imidazolium salt and [Ir(COD)Cl] 2 via a cascade of deprotonation/C−H activation processes. Both experimental complexation chemistry and computational mechanistic investigation suggest that the large bite angle and π-rich character of the dpa Ar2 NHC are responsible for its facile complexation as a dianionic LX 2type CCC-pincer ligand precursor. The all-carbon ligated iridium(III) complex (4) bearing a π-conjugated ligand scaffold showed remarkably low oxidation potentials, which allows future investigations in its redox chemistry and photophysical properties.

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Section: Resultsmentioning

confidence: 98%

Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N-Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C–H Bond Activation

et al. 2021

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“…Triphenylphosphine selenide is the byproduct of this reaction, which was conveniently removed from the reaction mixture. Complexes 1-4 were characterized by elemental analysis, FT-IR, multinuclear NMR ( 1 H, 13 C, 11 B, 19 F and 31 P), and single-crystal X-ray techniques.…”

Section: Resultsmentioning

confidence: 99%

“…In 13 C NMR, the carbene carbon of 1-4 resonates around 187.6-187.7 ppm, which is considerably downfield shifted compared to L (154.4 ppm) and tetra coordinated Cu(I) complex [Cu(dptn)(dppe)] + (PF 6 À ), dptn = 2,4-dimethyl-8-phenyl-triazolo naphtyridine-9-ylidine, dppe = 1,2-bis(diphenylphosphino)ether (180.9 ppm). [12] The 31 P NMR chemical shift values of triphenylphosphines in 1-4 appeared around 4.50-4.59 ppm.…”

Section: Resultsmentioning

confidence: 99%

“…[7,8] Besides, Cu-NHC complexes can also be used as NHC transfer agents. [9] In addition, the phosphine coordinated Cu-NHCs have demonstrated their wide range of structural aspects, [10][11][12] photo luminescence properties [13,14] and catalytic application in cycloaddition of azide-alkyne reaction, [15] tandem alkylation/arylation of primary phosphines, [16] double hydro phosphorating of terminal alkynes [17] and isocyanates [18] and kinetic resolution of aziridines. [19] Phosphine coordinated Cu(I)NHC complexes can be synthesized by various synthetic routes.…”

Section: Introductionmentioning

confidence: 99%

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A Simple and Fast Access to Phosphine‐Substituted Copper(I)‐Carbene Complexes via C=Se Bond Cleavage Reaction

Veerapathiran

Prabusankar

2023

Chemistry An Asian Journal

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Phosphine coordinated copper(I)-N-heterocyclic carbene complexes have emerged as an efficient material in catalysis and light-emitting applications. In this study, a gentle and sustainable approach to the copper(I)-carbene phosphine complexes is reported through an efficient C=Se activation protocol. The complexes [(Py^NHC)Cu(PPh 3 ) 2 ]X, X = BF 4 (1), ClO 4 (2), PF 6 (3) and OTf (4); Py^NHC = 3isopropyl-1-(pyridin-2-yl)-imidazol-2-ylidene, and [(Py^NHC)Cu(PPh 3 )(X)], X = Br (5) and I ( 6) have been synthesized by treating 1-isopropyl-3-(pyridin-2-yl)-imidazole-2-selone with corresponding copper(I) precursors and triphenylphosphine. In this synthetic strategy, N-heterocyclic carbene gets transferred from N-heterocyclic selone through a C=Se bond cleavage reaction to form copper(I) complexes within five minutes at room temperature. In addition, the mechanism responsible for the C=Se bond cleavage reaction has been fully investigated. These reactions are not sensitive to moisture and oxygen.

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“…It should be noticed that the formation of the complexes with two identical Group 11 metal atoms bridged by a carbene ligand is well known [231][232][233][234][235][236][237][238][239][240][241][242][243][244]. At the same time, the examples of similar heterometallic systems have not been found, which can indirectly evidence their low stability.…”

Section: Possible Mechanisms and Driving Forces Of Transmetalation And Related Processesmentioning

confidence: 99%

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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The carbene transfer from N-heterocyclic carbene complexes of Group 11 metals (NHC-M C ) (especially silver and copper) to other metals is considered a convenient and universal, sometimes having no alternative, method for the synthesis of a wide range of important N-heterocyclic carbene complexes of transition metals. As the number of successful examples of transmetalation with the formation of the target product has increased, the data were accumulated on alternative or unexpected results of the interaction of NHC-M C complexes with compounds of other metals. This review considers the examples of NHC-M C reactions with compounds of other metals which proceed with a change in the metals oxidation state, conversion of (NHC)M C X into cationic homoleptic [(NHC) 2 M C ] + forms, transmetalation retaining the other metal in the coordination sphere of the product, or formation of heterometallic adducts preserving the M C -C carbene bond, rather than these occurring according to the standard reaction pathway. Unusual "reverse" carbene transfer reactions have been considered separately. The review material reveals a promising new synthetic potential of NHC-M C in the reactions with other metals and discusses the possible mechanisms and driving forces of such transformations. The most important aspects of the application of the obtained products, primarily in various catalytic processes, have been considered as well.

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Bis(diphenylphosphinyl)-functionalized dipyrido-annulated NHC towards copper(i) and silver(i)

Abstract: Sterically rigid bis(phosphinyl)dipyrido-annulated NHC coordinates with Ag(i) and Cu(i) centres to form luminescent multinuclear complexes.

Cited by 8 publications

References 37 publications

Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N-Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C–H Bond Activation

Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N-Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C–H Bond Activation

A Simple and Fast Access to Phosphine‐Substituted Copper(I)‐Carbene Complexes via C=Se Bond Cleavage Reaction

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

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