Arylnickel(III) species containing nitrogen trioxide, nitrogen dioxide, and thiocyanate ligands. ESR data and the x-ray crystal structure of hexacoordinate (pyridine)bis(thiocyanato)[o,o'-bis{(dimethylamino)methyl}phenyl]nickel(III)

Koten, G. van; Grove, David M.; Mul, P.; Zeijden, A. A. H. Van Der; Terheijden, J.; Zoutberg, Martin C.; Stam, C. H.

doi:10.1021/om00133a022

Cited by 58 publications

(25 citation statements)

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“…X-ray quality crystals of 2 were obtained from THF/pentane, and the crystal structure shows the presence of a Ni III center that adopts a distorted octahedral geometry with an average axial Ni–N amine bond length of 2.246 Å and a shorter average equatorial Ni–N pyridyl bond length of 1.988 Å (Figure ). These values are consistent with our previously reported organometallic ( R N4)Ni III complexes (Ni–N amine bond lengths of 2.212–2.431 Å, Ni–N pyridyl bond lengths of 1.903−1.965 Å), , as well as other reported six-coordinate Ni III complexes. , Similarly, an average Ni–C Me bond length of 1.983 Å is consistent with the other structurally characterized Ni III −alkyl complexes reported (1.923, 1.994, 2.011 Å, 2.015, and 2.039 Å). − The CV of 2 in MeCN reveals a pseudoreversible oxidation wave at ∼0 V vs Fc + /Fc, followed by an irreversible oxidation at 0.36 V (Figure S2). The former reversible redox events suggests that the Ni IV oxidation state may be accessible, yet the one-electron oxidized species derived from 2 likely undergoes a rapid chemical reaction such as reductive elimination (vide infra), and the resulting Ni product could give rise to the higher potential irreversible oxidation (i.e., an ECE electrochemical mechanism).…”

Section: Results and Discussionsupporting

confidence: 93%

Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon–Carbon Bond Formation Reactions

et al. 2016

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Nickel-catalyzed cross-coupling reactions are experiencing a dramatic resurgence in recent years given their ability to employ a wider range of electrophiles as well as promote stereospecific or stereoselective transformations. In contrast to the extensively studied Pd catalysts that generally employ diamagnetic intermediates, Ni systems can more easily access various oxidation states including odd-electron configurations. For example, organometallic Ni intermediates with aryl and/or alkyl ligands are commonly proposed as the active intermediates in cross-coupling reactions. Herein, we report the first isolated Ni-dialkyl complex and show that this species is involved in stoichiometric and catalytic C-C bond formation reactions. Interestingly, the rate of C-C bond formation from a Ni center is enhanced in the presence of an oxidant, suggesting the involvement of transient Ni species. Indeed, such a Ni species was observed and characterized spectroscopically for a nickelacycle system. Overall, these studies suggest that both Ni and Ni species could play an important role in a range of Ni-catalyzed cross-coupling reactions, especially those involving alkyl substrates.

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Section: Results and Discussionsupporting

confidence: 93%

Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon–Carbon Bond Formation Reactions

et al. 2016

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“…The bond lengths are consistent with reported nickel(III) complexes. The EPR spectrum of 2 c shows a rhombic signal with g av =2.20 close to those of other known arylnickel(III) complexes of octahedral geometry . Most importantly, Ni III complex 2 c displays an EPR spectrum that is very similar to that of 2 b ( g av =2.20), which further supports our assignments of complexes 2 a and 2 b .…”

Section: Methodssupporting

confidence: 82%

Carbon–Fluorine Reductive Elimination from Nickel(III) Complexes

Lee

Ritter

2017

Angewandte Chemie

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“…Superhyperfine coupling to the two axial nitrogen atoms (I = 1), primarily in the gz direction (A2N = 18.5 G) was observed, consistent with formation of d 7 Ni III species with a S = 1/2 ground state in which the unpaired electron occupies primarily the dz 2 orbital of the Ni center. [47][48][49][50] Additionally, the DFT calculated spin density supports a metal-based radical description for 1 + , and the predominant dz 2 character of the unpaired electron (Figure 2b). The UV-visible absorption spectra of 1 and 1 + were obtained in MeCN (Figure 3, top).…”

Section: Resultssupporting

confidence: 64%

Photoreductive Chlorine Elimination from a Ni(III)Cl2 Complex Supported by a Tetradentate Pyridinophane Ligand

Na¹,

Watson²,

Tang³

et al. 2021

Preprint

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Herein we report the isolation, characterization, and photoreactivity of a stable NiIII dichloride complex supported by a tetradentate pyridinophane N-donor ligand. Upon irradiation, this complex undergoes an efficient photoreductive chlorine elimination reaction, both in solution and the solid-state. Subsequently, the NiIIICl2 <a>species can be regenerated via a reaction with PhICl2</a>.

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Arylnickel(III) species containing nitrogen trioxide, nitrogen dioxide, and thiocyanate ligands. ESR data and the x-ray crystal structure of hexacoordinate (pyridine)bis(thiocyanato)[o,o'-bis{(dimethylamino)methyl}phenyl]nickel(III)

Cited by 58 publications

References 1 publication

Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon–Carbon Bond Formation Reactions

Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon–Carbon Bond Formation Reactions

Carbon–Fluorine Reductive Elimination from Nickel(III) Complexes

Photoreductive Chlorine Elimination from a Ni(III)Cl2 Complex Supported by a Tetradentate Pyridinophane Ligand

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