Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes.

Dicopper complexes templated by dinucleating, pacman dipyrrin ligand scaffolds (Mesdmx, tBudmx: dimethylxanthine-bridged, cofacial bis-dipyrrin) were synthesized by deprotonation/metalation with mesitylcopper (CuMes; Mes: mesityl) or by transmetalation with cuprous precursors from the corresponding deprotonated ligand. Neutral imide complexes (Rdmx)Cu2(µ2-NAr) (R: Mes, tBu; Ar: 4-MeOC6H4, 3,5-(F3C)2C6H3) were synthesized by treatment of the corresponding dicuprous complexes with aryl azides. While one-electron reduction of (Mesdmx)Cu2(µ2-N(C6H4OMe)) with potassium graphite initiates an intramolecular, benzylic C-H amination at room temperature, chemical reduction of (tBudmx)Cu2(µ2-NAr) leads to isolable [(tBudmx)Cu2(µ2-NAr)]- product salts. The electronic structures of the thermally robust [(tBudmx)Cu2(µ2-NAr)]0/- complexes were assessed by variable-temperature electron paramagnetic resonance spectroscopy, X-ray absorption spectroscopy (Cu L2,3/K-edge, N K-edge), optical spectroscopy, and DFT/CASSCF calculations. These data indicate that the formally Class IIIA mixed valence complexes of the type [(Rdmx)Cu2(µ2-NAr)]- feature significant NAr-localized spin following reduction from electronic population of the [Cu2(µ2-NAr)] π* manifold, contrasting previous methods for engendering iminyl character through chemical oxidation. The reactivity of the isolable imido and iminyl complexes are examined for prototypical radical-promoted reactivity (e.g., nitrene transfer and H-atom abstraction), where the divergent reactivity is rationalized by the relative degree of N-radical character afforded from different aryl substituents.

The Myth of d8 Copper(III).

Seventeen Cu complexes with formal oxidation states ranging from CuI to CuIII are investigated through the use of multiedge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations. Analysis reveals that the metal-ligand bonding in high-valent, formally CuIII species is extremely covalent, resulting in Cu K-edge and L2,3-edge spectra whose features have energies that complicate physical oxidation state assignment. Covalency analysis of the Cu L2,3-edge data reveals that all formally CuIII species have significantly diminished Cu d-character in their lowest unoccupied molecular orbitals (LUMOs). DFT calculations provide further validation of the orbital composition analysis, and excellent agreement is found between the calculated and experimental results. The finding that Cu has limited capacity to be oxidized necessitates localization of electron hole character on the supporting ligands; consequently, the physical d8 description for these formally CuIII species is inaccurate. This study provides an alternative explanation for the competence of formally CuIII species in transformations that are traditionally described as metal-centered, 2-electron CuI/CuIII redox processes.

Reversible Ligand-Centered Reduction in Low-Coordinate Iron Formazanate Complexes.

Coordination of redox-active ligands to metals is a compelling strategy for making reduced complexes more accessible. In this work, we explore the use of redox-active formazanate ligands in low-coordinate iron chemistry. Reduction of an iron(II) precursor occurs at milder potentials than analogous non-redox-active ß-diketiminate complexes, and the reduced three-coordinate formazanate-iron compound is characterized in detail. Structural, spectroscopic, and computational analysis show that the formazanate ligand undergoes reversible ligand-centered reduction to form a formazanate radical dianion in the reduced species. The less negative reduction potential of the reduced low-coordinate iron formazanate complex leads to distinctive reactivity with formation of a new N-I bond that is not seen with the ß-diketiminate analogue. Thus, the storage of an electron on the supporting ligand changes the redox potential and enhances certain reactivity.

Chalcogen Impact on Covalency within Molecular [Cu3(µ3-E)]3+ Clusters (E = O, S, Se): A Synthetic, Spectroscopic, and Computational Study.

Reaction of the tricopper(I)-dinitrogen tris(ß-diketiminate) cyclophane, Cu3(N2)L, with O-atom-transfer reagents or elemental Se affords the oxido-bridged tricopper complex Cu3(µ3-O)L (2) or the corresponding Cu3(µ3-Se)L (4), respectively. For 2 and 4, incorporation of the bridging chalcogen donor was supported by electrospray ionization mass spectrometry and K-edge X-ray absorption spectroscopy (XAS) data. Cu L2,3-edge X-ray absorption data quantify 49.5% Cu 3d character in the lowest unoccupied molecular orbital of 2, with Cu 3d participation decreasing to 33.0% in 4 and 40.8% in the related sulfide cluster Cu3(µ3-S)L (3). Multiedge XAS and UV/visible/near-IR spectra are employed to benchmark density functional theory calculations, which describe the copper-chalcogen interactions as highly covalent across the series of [Cu3(µ-E)]3+ clusters. This result highlights that the metal-ligand covalency is not reserved for more formally oxidized metal centers (i.e., CuIII + O2- vs CuII + O-) but rather is a significant contributor even at more typical ligand-field cases (i.e., Cu3II/II/I + E2-). This bonding is reminiscent of that observed in p-block elements rather than in early-transition-metal complexes.

Electronic Structural Analysis of Copper(II)-TEMPO/ABNO Complexes Provides Evidence for Copper(I)-Oxoammonium Character.

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and the present study probes this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L2,3-edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-driven alcohol oxidation reactions, with similar findings. Collectively, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co-catalyst system.

Direct Comparison of C-H Bond Amination Efficacy through Manipulation of Nitrogen-Valence Centered Redox: Imido versus Iminyl.

Reduction of previously reported iminyl radical (ArL)FeCl(•N(C6H4-p-tBu)) (2) with potassium graphite furnished the corresponding high-spin (S = 5/2) imido (ArL)Fe(N(C6H4-p-tBu)) (3) (ArL = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin). Oxidation of the three-coordinate imido (ArL)Fe(NAd) (5) with chlorotriphenylmethane afforded (ArL)FeCl(•NAd) (6) with concomitant expulsion of Ph3C(C6H5)CPh2. The respective aryl/alkyl imido/iminyl pairs (3, 2; 5, 6) have been characterized by EPR, zero-field 57Fe Mössbauer, magnetometry, single crystal X-ray diffraction, XAS, and EXAFS for 6. The high-spin (S = 5/2) imidos exhibit characteristically short Fe-N bonds (3: 1.708(4) Å; 5: 1.674(11) Å), whereas the corresponding iminyls exhibit elongated Fe-N bonds (2: 1.768(2) Å; 6: 1.761(6) Å). Comparison of the pre-edge absorption feature (1s → 3d) in the X-ray absorption spectra reveals that the four imido/iminyl complexes share a common iron oxidation level consistent with a ferric formulation (3: 7111.5 eV, 2: 7111.5 eV; 5: 7112.2 eV, 6: 7112.4 eV) as compared with a ferrous amine adduct (ArL)FeCl(NH2Ad) (7: 7110.3 eV). N K-edge X-ray absorption spectra reveal a common low-energy absorption present only for the iminyl species 2 (394.5 eV) and 6 (394.8 eV) that was assigned as a N 1s promotion into a N-localized, singly occupied iminyl orbital. Kinetic analysis of the reaction between the respective iron imido and iminyl complexes with toluene yielded the following activation parameters: Ea (kcal/mol) 3: 12.1, 2: 9.2; 5: 11.5, 6: 7.1. The attenuation of the Fe-N bond interaction on oxidation from an imido to an iminyl complex leads to a reduced enthalpic barrier [Δ(ΔH‡) ≈ 5 kcal/mol]; the alkyl iminyl 6 has a reduced enthalpic barrier (1.84 kcal/mol) as compared with the aryl iminyl 2 (3.84 kcal/mol), consistent with iminyl radical delocalization into the aryl substituent in 2 as compared with 6.

Spectroscopic Evidence for a 3d(10) Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF3)4](1-).

The contested electronic structure of [Cu(CF3)4](1-) is investigated with UV/visible/near IR spectroscopy, Cu K-edge X-ray absorption spectroscopy, and 1s2p resonant inelastic X-ray scattering. These data, supported by density functional theory, multiplet theory, and multireference calculations, support a ground state electronic configuration in which the lowest unoccupied orbital is of predominantly trifluoromethyl character. The consensus 3d(10) configuration features an inverted ligand field in which all five metal-localized molecular orbitals are located at lower energy relative to the trifluoromethyl-centered σ orbitals.

Scrutinizing metal-ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy.

Nitrogen K-edge X-ray absorption spectra (XAS) were obtained for 19 transition metal complexes bearing bipyridine, ethylenediamine, ammine, and nitride ligands. Time-dependent density functional theory (TDDFT) and DFT/restricted open configuration interaction singles (DFT/ROCIS) calculations were found to predict relative N K-edge XAS peak energies with good fidelity to experiment. The average difference (|ΔE|) between experimental and linear corrected calculated energies were found to be 0.55 ± 0.05 eV and 0.46 ± 0.04 eV, respectively, using the B3LYP hybrid density functional and scalar relativistically recontracted ZORA-def2-TZVP(-f) basis set. Deconvolution of these global correlations into individual N-donor ligand classes gave improved agreement between experiment and theory with |ΔE| less than 0.4 eV for all ligand classes in the case of DFT/ROCIS. In addition, calibration method-dependent values for the N 1s → 2p radial dipole integral of 25.4 ± 1.7 and 26.8 ± 1.9 are obtained, affording means to estimate the nitrogen 2p character in unfilled frontier molecular orbitals. For the complexes studied, nitrogen covalency values correlate well to those calculated by hybrid DFT with an R 2 = 0.92 ± 0.01. Additionally, as a test case, a well-characterized PNP ligand framework (PNP = N[2-P(CHMe2)2-4-methylphenyl]2 1-) coordinated to NiII is investigated for its ability to act as a redox non-innocent ligand. Upon oxidation of (PNP)NiCl with [FeCp2](OTf) to its radical cation, [(PNP)NiCl](OTf) (OTf = triflate), a new low-energy feature emerges in the N K-edge XAS spectra. This feature is assigned as N 1s to a PNP-localized acceptor orbital exhibiting 27 ± 2% N 2p aminyl radical character, obtained using the aforementioned nitrogen covalency calibration. Combined, these data showcase a direct spectroscopic means of identifying redox-active N-donor ligands and also estimating nitrogen 2p covalency of frontier molecular orbitals in transition metal complexes.

Synthesis, characterization and C-H amination reactivity of nickel iminyl complexes.

Metalation of the deprotonated dipyrrin (AdFL)Li with NiCl2(py)2 afforded the divalent Ni product (AdFL)NiCl(py)2 (1) (AdFL: 1,9-di(1-adamantyl)-5-perfluorophenyldipyrrin; py: pyridine). To generate a reactive synthon on which to explore oxidative group transfer, we used potassium graphite to reduce 1, affording the monovalent Ni synthon (AdFL)Ni(py) (2) and concomitant production of a stoichiometric equivalent of KCl and pyridine. Slow addition of mesityl- or 1-adamantylazide in benzene to 2 afforded the oxidized Ni complexes (AdFL)Ni(NMes) (3) and (AdFL)Ni(NAd) (4), respectively. Both 3 and 4 were characterized by multinuclear NMR, EPR, magnetometry, single-crystal X-ray crystallography, theoretical calculations, and X-ray absorption spectroscopies to provide a detailed electronic structure picture of the nitrenoid adducts. X-ray absorption near edge spectroscopy (XANES) on the Ni reveals higher energy Ni 1s → 3d transitions (3: 8333.2 eV; 4: 8333.4 eV) than NiI or unambiguous NiII analogues. N K-edge X-ray absorption spectroscopy performed on 3 and 4 reveals a common low-energy absorption present only for 3 and 4 (395.4 eV) that was assigned via TDDFT as an N 1s promotion into a predominantly N-localized, singly occupied orbital, akin to metal-supported iminyl complexes reported for iron. On the continuum of imido (i.e., NR2-) to iminyl (i.e., 2NR-) formulations, the complexes are best described as NiII-bound iminyl species given the N K-edge and TDDFT results. Given the open-shell configuration (S = 1/2) of the iminyl adducts, we then examined their propensity to undergo nitrenoid-group transfer to organic substrates. The adamantyl complex 4 readily consumes 1,4-cyclohexadiene (CHD) via H-atom abstraction to afford the amide (AdFL)Ni(NHAd) (5), whereas no reaction was observed upon treatment of the mesityl variant 3 with excess amount of CHD over 3 hours. Toluene can be functionalized by 4 at room temperature, exclusively affording the N-1-adamantyl-benzylidene (6). Slow addition of the organoazide substrate (4-azidobutyl)benzene (7) with 2 exclusively forms 4-phenylbutanenitrile (8) as opposed to an intramolecular cyclized pyrrolidine, resulting from facile ß-H elimination outcompeting H-atom abstraction from the benzylic position, followed by rapid H2-elimination from the intermediate Ni hydride ketimide intermediate.