Accessing perfluoroalkyl nickel(<scp>ii</scp>), (<scp>iii</scp>), and (<scp>iv</scp>) complexes bearing a readily attached [C4F8] ligand

Yu, Siqi; Dudkina, Yulia B.; Wang, H.; Kholin, Kirill V.; Kadirov, Marsil K.; Budnikova, Yulia H.; Vicic, David A.

doi:10.1039/c5dt01771h

Cited by 47 publications

(67 citation statements)

References 39 publications

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“…It was found that the addition of terpyridine to [Ni(MeCN)2(C4F8)] 12 led cleanly to the formation of [Ni(tpy)(C4F8)] 14 (Scheme 9) [55]. Surprisingly, in the solid state, the terpyridine ligand in 14 coordinates to nickel in a η 2 -fashion.…”

Section: Electrochemistry and Character Of The Trivalent Species [Ni(mentioning

confidence: 99%

“…Terpyridine is known to bind to more than one metal center [56][57][58][59][60][61], but 13 represented the first such adduct with nickel. [55]. Surprisingly, in the solid state, the terpyridine ligand in 14 coordinates to nickel in a η 2 -fashion.…”

Section: Electrochemistry and Character Of The Trivalent Species [Ni(mentioning

confidence: 99%

“…Synthesis of tpy nickel complexes bearing a readily attached [C 4 F 8 2− ] ligand, adopted from ref. [55].…”

Section: Further Ni-tpy Catalyzed C-c Cross-coupling Reactionsmentioning

confidence: 99%

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Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

2018

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Abstract:In recent years, nickel has entered the stage for catalyzed C-C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2 :6 ,2 -terpyridine (tpy) stands as an excellent example of these ligands. This review summarizes research that has been devoted to exploring the mechanistic details in catalyzed C-C cross-coupling reactions using tpy-based nickel systems.

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Section: Electrochemistry and Character Of The Trivalent Species [Ni(mentioning

confidence: 99%

Section: Electrochemistry and Character Of The Trivalent Species [Ni(mentioning

confidence: 99%

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Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

2018

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“…To understand the mechanism of HOR on the anode side of the FC,t he compound was investigated using electron spin resonance (ESR). ESR proved to be an effective methodf or the exact magnetic resonance identification of free radicals [24,25] and transition metal ions in solutions, [26] for studies of classical micellar solutions of surfactants, [27] amphiphilic calix [4]arenes, [28] andf or intermediates of ESR electrochemical transformations. [29][30][31][32][33][34][35] In order to study the nature of the reduced forms of the catalytic complex the complex was studied using ESR during reduction by molecular hydrogen and the electrochemical reduction at the potential of the first peak.…”

Section: Resultsmentioning

confidence: 99%

Organometallic Polymer Electrolyte Membrane Fuel Cell Bis‐Ligand Nickel(Ii) Complex of 1,5‐Di‐P‐Tolyl‐3,7‐Dipyridine‐1,5,3,7‐Diazadiphosphacyclo‐Octane Catalyst

et al. 2018

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A 1,4‐Diaza‐3.7‐diphosphacyclo‐otane organometallic bis‐ligand nickel(II) complex [Ni(PPy2Np‐Tol2)2]2+2.[BF4]− on Vulcan XC‐72 (C) functions as both the cathode and anode catalysts in polymer electrolyte membrane fuel cell (PEMFC). In a PEMFC using Ni(Py‐p‐Tol)/C at the anode and Pt/C at the cathode the power density is shown to reach 14.66 mW cm−2, which is the highest power density of the none‐noble organometallic analogs. Based on the data produced using independent physico‐chemical methods, the mechanisms of the hydrogen oxidation and oxygen reduction reactions (HOR and ORR) on the anode and cathode sides of PEMFC, respectively, are reported.

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“…Fortuitous crystallization in MeCN/Ether provided X-Ray quality crystals. 19 S7 . 2 The [Cu(CF3)4]core was described as having "surprising" 2 stability as it possessed a rare and formally copper(III) center.…”

Section: Generation Of [Pph4]2[( 2 -So4)ni IV (Cf3)4] (8)mentioning

confidence: 99%

[(MeCN)Ni(CF3)3]1– and [Ni(CF3)4]2– : Foundations Towards the Development of Trifluoromethylations at Unsupported Nickel

Shreiber¹,

DiMucci²,

Khrizanforov³

et al. 2020

Preprint

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The nickel anions [(MeCN)Ni(CF3)3]1– and [Ni(CF3)4]2– were prepared by formal addition of three and four equivalents of [AgCF3] to [(dme)NiBr2] in the presence of supporting [PPh4] counter-ion. Detailed insights into the electronic properties of these new compounds were obtained through the use of density functional theory (DFT) calculations, spectroscopy-oriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry. The data collectively show that trifluoromethyl complexes of nickel, even in the most common oxidation state of nickel(II), are highly covalent systems whereby a hole is distributed on the trifluoromethyl ligands and surprisingly rendering the metal to a physically more reduced state. In the cases of [(MeCN)Ni(CF3)3]1– and [Ni(CF3)4]2–, these complexes are better described as physically d9 metal complexes. [(MeCN)Ni(CF3)3]1– is electrophilic and reacts with other nucleophiles like phenoxide to yield the unsupported [(PhO)Ni(CF3)3]2– salt, revealing the broader potential of [(MeCN)Ni(CF3)3]1– in the development of ligandless trifluoromethylations at nickel. Proof-in-principle experiments show that reaction of [(MeCN)Ni(CF3)3]1– with an aryl iodonium salt yields trifluoromethylated arene, presumably via a high valent, unsupported, and formally organonickel(IV) intermediate. Evidence for the feasibility of such intermediates is provided with the structurally characterized [Ni(CF3)4(SO4)][PPh4]2, which was derived through the two electron oxidation of [Ni(CF3)4]2–.

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Accessing perfluoroalkyl nickel(ii), (iii), and (iv) complexes bearing a readily attached [C₄F₈] ligand

Cited by 47 publications

References 39 publications

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Organometallic Polymer Electrolyte Membrane Fuel Cell Bis‐Ligand Nickel(Ii) Complex of 1,5‐Di‐P‐Tolyl‐3,7‐Dipyridine‐1,5,3,7‐Diazadiphosphacyclo‐Octane Catalyst

[(MeCN)Ni(CF3)3]1– and [Ni(CF3)4]2– : Foundations Towards the Development of Trifluoromethylations at Unsupported Nickel

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Accessing perfluoroalkyl nickel(ii), (iii), and (iv) complexes bearing a readily attached [C4F8] ligand

Cited by 47 publications

References 39 publications

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Organometallic Polymer Electrolyte Membrane Fuel Cell Bis‐Ligand Nickel(Ii) Complex of 1,5‐Di‐P‐Tolyl‐3,7‐Dipyridine‐1,5,3,7‐Diazadiphosphacyclo‐Octane Catalyst

[(MeCN)Ni(CF3)3]1– and [Ni(CF3)4]2– : Foundations Towards the Development of Trifluoromethylations at Unsupported Nickel

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Accessing perfluoroalkyl nickel(ii), (iii), and (iv) complexes bearing a readily attached [C₄F₈] ligand