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Ribas, Xavi; Jackson, Deanne A.; Donnadieu, Bruno; Mahı́a, José; Parella, Teodor; Xifra, Raül; Hedman, Britt; Llobet, Antoni; Stack, T. Daniel P.

doi:10.1002/1521-3757(20021202)114:23<4549::aid-ange11114549>3.0.co;2-8

Cited by 46 publications

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“…Having a copper coordination environment similar to that with the bdiketiminate ligand and having been well characterized with respect to its electrochemistry, a copper complex supported by a triazamacrocyclic ligand was chosen as the reference system. 46 Its measured Cu(III)/Cu(II) reduction potential was −0.271 V vs. SHE, whereas the computed reduction potential was 0.485 V, implying the correction factor to be −0.76 V. View Online of DFT is particularly relevant to calculations on complexes between Cu(I) and dioxygen. 48 These species typically possess nontrivial degrees of Cu(II)-superoxo character, which may be considered to be biradical, with one electron localized to Cu(II) and the other to superoxide.…”

Section: Computational Methods: a Density Functional Calculationsmentioning

confidence: 99%

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes

et al. 2006

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Copper(i) complexes with the beta-diketiminate ligands HC{C(R)N(Dipp)}{C(R')N(Dipp)}(-) (Dipp = C(6)H(3)(i)Pr(2-)2,6; L(1), R = CF(3), R' = CH(3); L(2), R = R' = CF(3)) have been isolated and fully characterized. On the basis of X-ray structural comparisons with the previously reported complex LCu(CH(3)CN) (L = HC{C(CH(3))N(Dipp)}(2)(-)), the ligand environments at the copper centers in the analogous nitrile adducts with L(1) and L(2) impose similar steric demands. L(1)Cu(CH(3)CN) reacts instantaneously at low temperature with O(2) to form a thermally-unstable intermediate with an isotope-sensitive vibration at 977 cm(-1) (928 cm(-1) with (18)O(2)), in accord with the peroxo O-O stretch associated with side-on coordination for LCu(O(2)). However, L(2)Cu(CH(3)CN) is unreactive toward O(2) even at room temperature. Evaluation of the redox potentials of the nitrile adducts and the CO stretching frequencies of the carbon monoxide adducts revealed an incremental adjustment of the electronic environment at the copper center that correlated with the extent of ligand fluorination. Furthermore, theoretical calculations (DFT, CASPT2) predicted that an increasing extent of Cu(ii)-superoxo character and end-on coordination of the O(2) moiety in the Cu/O(2) product (L(2) > L(1) > L) are accompanied by increases in the free energy for the oxygenation reaction, with L(2) unable to support a Cu/O(2) intermediate. Calculations also predict the 1 : 1 Cu/O(2) adducts to be unreactive with respect to hydrogen atom abstraction from hydrocarbon substrates on the basis of their stability towards both reduction and protonation.

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Section: Computational Methods: a Density Functional Calculationsmentioning

confidence: 99%

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes

et al. 2006

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“…16a The reactions proceed via Cu(III) intermediates, thus showing that C-F reductive elimination from Cu(III) is possible under very mild conditions. 7b Given that aminoquinoline amides stabilize high oxidation states in transition metals, 14d it is likely that copper-catalyzed aminoquinoline amide fluorination also proceeds via Cu(III) intermediates.…”

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confidence: 99%

“…14a Recently copper-catalyzed sulfenylation and amination of C-H bonds in 8-aminoquinoline benzamides and benzylamine picolinamides was demonstrated. 14b,c We hypothesized that 8-aminoquinoline and picolinic acid auxiliaries would promote copper-catalyzed ortho -fluorination of sp 2 C-H bonds based on the following considerations: (1) copper-catalyzed aryl halide fluorination has been reported in a macrocyclic polyamine system, 16a (2) copper-promoted C-H activation has been reported in the same system, 16b and (3) it appears that both macrocyclic amine and 8-aminoquinoline benzamide ligands stabilize high-valent copper intermediates.…”

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confidence: 99%

Copper-Catalyzed, Directing Group-Assisted Fluorination of Arene and Heteroarene C–H Bonds

2013

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We have developed a method for direct, copper-catalyzed, auxiliary-assisted fluorination of β-sp2 C-H bonds of benzoic acid derivatives and γ-sp2 C-H bonds of α,α-disubstituted benzylamine derivatives. The reaction employs CuI catalyst, AgF fluoride source, and DMF, pyridine, or DMPU solvent at moderately elevated temperatures. Selective mono- or difluorination can be achieved by simply changing reaction conditions. The method shows excellent functional group tolerance and provides a straightforward way for the preparation of ortho-fluorinated benzoic acids.

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“…3 Thus the resting state and also reactive form of lithium organocuprates ("R 2 CuLi", R = organo group) in non- employed a triaza-macrocyclic ligand to yield the first example of an isolable Cu(III) monoaryl species. 22 …”

Section: Figure 1 Cip (I) and Ssip (Ii) Structures Of Lithium Homocumentioning

confidence: 99%

Functionalized Organocuprates: Structures of Lithium and Magnesium Grignard 2-Methoxyphenylcuprates

et al. 2012

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Cited by 46 publications

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Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes

Copper-Catalyzed, Directing Group-Assisted Fluorination of Arene and Heteroarene C–H Bonds

Functionalized Organocuprates: Structures of Lithium and Magnesium Grignard 2-Methoxyphenylcuprates

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Cited by 46 publications

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Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O2-reactivity of mononuclear Cu(i) complexes

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O2-reactivity of mononuclear Cu(i) complexes

Copper-Catalyzed, Directing Group-Assisted Fluorination of Arene and Heteroarene C–H Bonds

Functionalized Organocuprates: Structures of Lithium and Magnesium Grignard 2-Methoxyphenylcuprates

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Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes

Electronic tuning of β-diketiminate ligands with fluorinated substituents: effects on the O₂-reactivity of mononuclear Cu(i) complexes