ABSTRACT
Copper(III) aryl species are widely proposed as intermediates in Cu-catalyzed C-C and C-heteroatom bond formation reactions. Despite their wide utility, mechanistic aspects of C-heteroatom formation at CuIII centers as well as factors that lead to byproducts, e.g., Ar-H, Ar-Ar, remain elusive due to the rarity of discrete CuIII-Ar complexes. Herein, we report the synthesis and reactivity of a series of CuII and CuIII aryl complexes that closely mimic the intermediates in Cu-catalyzed C-N coupling reactions. Copper(II) aryl complexes [TBA][LCuII-ArR] were synthesized via the treatment of CuII with a range of aryl donors, such as ZnAr2R, TMS-ArR, and ArR-Bpin. Oxidation of [TBA][LCuII-ArR] produces formal copper(III) aryl complexes LCuIII-ArR. Treatment of copper(III) aryl complexes with neutral nitrogen nucleophiles produces the C-N coupling product in up to 64% yield, along with commonly observed byproducts, such as Ar-H and Ar-Ar. Hammett analysis of the C-N bond formation performed with various N-nucleophiles shows a ρ value of -1.66, consistent with the electrophilic character of LCuIII-ArR. We propose mechanisms for common side reactions in Cu-catalyzed coupling reactions that lead to the formation of Ar-Ar and Ar-H.
ABSTRACT
Despite the growing interest in the synthesis of fluorinated organic compounds, few reactions are able to incorporate fluoride ions directly into alkyl C-H bonds. Here, we report the C(sp3)-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, LCuF, along with its chloride and bromide analogues, LCuCl and LCuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized with single-crystal X-ray diffraction, X-ray absorption spectroscopy, UV-vis spectroscopy, and 1H nuclear magnetic resonance spectroscopy. Quantum chemical calculations reveal significant halide radical character for all complexes, suggesting their ability to initiate and terminate a C(sp3)-H halogenation sequence by sequential hydrogen atom abstraction (HAA) and radical capture. The capability of HAA by the formally copper(III) halide complexes was explored with 9,10-dihydroanthracene, revealing that LCuF exhibits rates 2 orders of magnitude higher than LCuCl and LCuBr. In contrast, all three complexes efficiently capture carbon radicals to afford C(sp3)-halogen bonds. Mechanistic investigation of radical capture with a triphenylmethyl radical revealed that LCuF proceeds through a concerted mechanism, while LCuCl and LCuBr follow a stepwise electron transfer-halide transfer pathway. The capability of LCuF to perform both hydrogen atom abstraction and radical capture was leveraged to enable fluorination of allylic and benzylic C-H bonds and α-C-H bonds of ethers at room temperature.
ABSTRACT
Treatment of a dicopper(I,I) complex with nitric oxide produces a dicopper µ-oxo, µ-nitrosyl complex [LCu2(µ-O)(µ-NO)]2+, representing the first structurally characterized µ-oxo, µ-nitrosyl metal complex. This compound can also be synthesized from the reaction of nitrite with an [LCuIICuI]3+ synthon. Full characterization of the thermal-sensitive [LCu2(µ-O)(µ-NO)]2+ complex with IR, EPR, and X-ray crystallography suggests a localized mixed-valent CuIII, CuII, O2-, NO- formulation. The [Cu2(µ-O)(µ-NO)]2+ core efficiently oxidizes exogenous substrates, such as phosphine, cyclohexadienes, and isochroman to afford phosphine oxide, benzene, and 1-isochromanone. Since both nitrite and nitric oxide are proposed oxidants in denitrifying methane oxidation, the oxidative reactivity of [Cu2(µ-O)(µ-NO)]2+ core is potentially relevant to anaerobic methane oxidation observed in methanotrophic archaea.
ABSTRACT
While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3 CuNO]- , with a {CuNO}10 electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3 CuNO]- was synthesized analogously, and both copper halonitrosyl complexes were characterized by X-ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a CuII -NO. ground state. Both [Cl3 CuNO]- and [Br3 CuNO]- release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.
ABSTRACT
High-valent metal oxo complexes are prototypical intermediates for the activation and hydroxylation of alkyl C-H bonds. Substituting the oxo ligand with other functional groups offers the opportunity for additional C-H functionalization beyond C-O bond formation. However, few species aside from metal oxo complexes have been reported to both activate and functionalize alkyl C-H bonds. We herein report the first example of an isolated copper(iii) cyanide complex (LCuIIICN) and its C-H cyanation reactivity. We found that the redox potential (E ox) of substrates, instead of C-H bond dissociation energy, is a key determinant of the rate of PCET, suggesting an oxidative asynchronous CPET or ETPT mechanism. Among substrates with the same BDEs, those with low redox potentials transfer H atoms up to a million-fold faster. Capitalizing on this mechanistic insight, we found that LCuIIICN is highly selective for cyanation of amines, which is predisposed to oxidative asynchronous or stepwise transfer of H+/e-. Our study demonstrates that the asynchronous effect of PCET is an appealing tool for controlling the selectivity of C-H functionalization.
ABSTRACT
Alkali-exchanged SSZ-13 adsorbents were investigated for their applicability in separating N2 from CO2 in flue gas streams using a dynamic breakthrough method. In contrast to IAST calculations based on equilibrium isotherms, K+ exchanged SSZ-13 was found to yield the best N2 productivity, comparable to Ni-MOF-74, under dynamic conditions where diffusion properties play a significant role. This was attributed to the selective, partial blockage of access to the chabazite cavities, enhancing the separation potential in a 15/85 CO2/N2 binary gas mixture.