Organic chemistry of subvalent transition complexes. 9. Oxidative addition of nickel(0) complexes to carbon-carbon bonds in biphenylene: formation of nickelole and 1,2-dinickelecin intermediates

Eisch, John J.; Piotrowski, A.; Han, Kyoung I.; Krüger, Carl; Tsay, Yi‐Hung

doi:10.1021/om00121a003

Cited by 149 publications

(118 citation statements)

References 3 publications

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“…[6,7] It was first determined that free biphenylene undergoes no reaction whatsoever with the mild nucleophiles M(PPh 3 ) 2 (C 2 H 4 ) (M Pt, Pd). However, the reactivity changed dramatically when Mn(CO) 3 was coordinated to one of the arene rings to give complex 1. It was found that Pt(PPh 3 ) 2 (C 2 H 4 ), as well as Pt(PPh 3 ) 3 , react completely in less than one minute at room temperature in dichloromethane solution to afford the metallacycle 2.…”

Section: à C Bond Activationmentioning

confidence: 99%

“…The arrows in Figure 1 indicate the particular bond to be cleaved by an appropriate metal nucleophile. In each case, the adjacent carbocyclic ring was coordinated to a metal fragment, most commonly Mn(CO) 3 . It is shown below that this leads to remarkable and in some cases unprecedented levels of activation for C À C, C À O, C À S, C À Se and N À H bonds.…”

Section: Introductionmentioning

confidence: 99%

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The Remote Activation of Chemical Bonds via Metal Coordination

Oh¹,

Yu²,

Li³

et al. 2003

Adv Synth Catal

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Section: à C Bond Activationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Remote Activation of Chemical Bonds via Metal Coordination

Oh¹,

Yu²,

Li³

et al. 2003

Adv Synth Catal

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“…Later, Eisch examined various nickel complexes for this reaction, and found that the ligands attached to the metal center of nickel complexes played a crucial role in the oxidative insertion into the strained C-C bond of 5 [15]. For example, complex Ni(COD) 2 was unreactive towards 5, whereas Ni(Et 3 P) 4 completely even at 0 • C. Importantly, a dibenzonickelole intermediate (9) was proposed to be involved in the reaction mechanism (Scheme 5).…”

Section: Pyrolysis And/or Metal-catalyzed Dimerization Of Biphenylenesmentioning

confidence: 99%

Synthesis of tetraphenylene derivatives and their recent advances

Han

Peng

Wong

2017

National Science Review

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“…Synthesis of Compound 3 using Pd 2 (dba) 3 and O 2 Compound 1-H (300 mg, 0.606 mmol, 1 equiv.) was dissolved in tetrahydrofuran (10 mL) and then transferred to a 20 mL scintillation vial.…”

Section: S7mentioning

confidence: 99%

“…Synthesis of Compound 2 6 Synthesis of Complex 3 using Pd(OAc) 2 6 Synthesis of Compound 3 using Pd 2 (dba) 3 UV/Vis Spectra Figure S47. Solution UV/Vis spectrum for 2 addition.…”

mentioning

confidence: 99%

Dioxygen Reduction by a Pd(0)–Hydroquinone Diphosphine Complex

Horak

Agapie

2016

J. Am. Chem. Soc.

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A novel p-terphenyl diphosphine ligand was synthesized with a noninnocent hydroquinone moiety as the central arene (1-H). Pseudo-tetrahedral 4-coordinate Ni0 and Pd0–quinone (2 and 3, respectively) complexes proved accessible by metalating 1-H with the corresponding M(OAc)2 precursors. O2 does not react with the Pd0–quinone species (3) and protonation occurs at the quinone moiety indicating that the coordinated oxidized quinonoid moiety prevents reactivity at the metal. A 2-coordinate Pd0–hydroquinone complex (4-H) was prepared using a one-pot metalation with PdII followed by reduction. The reduced quinonoid moiety in 4-H shows metal-coupled reactivity with small molecules. 4-H was capable of reducing a variety of substrates including dioxygen, nitric oxide, nitrous oxide, 1-azido adamantane, trimethylamine n-oxide, and 1,4-benzoquinone quantitatively producing 3 as the Pd-containing reaction product. Mechanistic investigations of dioxygen reduction revealed that the reaction proceeds through a η2-peroxo intermediate (Int1) at low temperatures followed by subsequent ligand oxidation at higher temperatures in a reaction that consumed half an equivalent of O2 and produced water as a final oxygenic byproduct. Control compounds with methyl protected phenolic moieties (4-Me), displaying a AgI center incapable of O2 binding (7-H) or a cationic Pd–H motif (6-H) allowed for the independent examination of potential reaction pathways. The reaction of 4-Me with dioxygen at low temperature produces a species (8-Me) analogous to Int1 demonstrating that initial dioxygen activation is an inner sphere Pd-based process where the hydroquinone moiety only subsequently participates in the reduction of O2, at higher temperatures, by H+/e– transfers.

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Organic chemistry of subvalent transition complexes. 9. Oxidative addition of nickel(0) complexes to carbon-carbon bonds in biphenylene: formation of nickelole and 1,2-dinickelecin intermediates

Cited by 149 publications

References 3 publications

The Remote Activation of Chemical Bonds via Metal Coordination

The Remote Activation of Chemical Bonds via Metal Coordination

Synthesis of tetraphenylene derivatives and their recent advances

Dioxygen Reduction by a Pd(0)–Hydroquinone Diphosphine Complex

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