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Transient Formation and Reactivity of a High-Valent Nickel(IV) Oxido Complex
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† Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands
‡ IQCC & Departament de Química, Universitat de Girona, Campus Montilivi (Ciències), 17003 Girona, Spain
# ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain
§ Sustainable Materials Characterisation, Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
*[email protected]
*[email protected]
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Journal of the American Chemical Society

Cite this: J. Am. Chem. Soc. 2017, 139, 25, 8718–8724
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https://doi.org/10.1021/jacs.7b04158
Published June 5, 2017

Copyright © 2017 American Chemical Society. This publication is licensed under CC-BY-NC-ND.

Abstract

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A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L)2Ni(II)2(μ-X)3]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L)2Ni(IV)2(μ-O)3]2+. Its structure and its reactivity with organic substrates are demonstrated through a combination of UV–vis absorption, resonance Raman, 1H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.

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Introduction

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Metalloenzymes are central to the functioning of biological systems, especially in oxidative transformations and protection against reactive oxygen species. (1) Fe-, Cu-, and Mn-dependent metalloenzymes have been studied extensively and have stimulated the design and synthesis of structural and functional model complexes, especially in the search for synthetic analogues of reactive bioinorganic intermediates. (2) Recently, attention has turned to synthetic nickel-based complexes due to both enzymes such as NOD (nickel oxide dismutase) (3) and their potential in the activation of small molecules, including H2O2, (4) mCPBA, (5) and NaOCl. (6) In the latter case, such complexes open the possibility to achieve selective alkane chlorination and alkane and alkene oxygenation.
Recently, several high-valent (Ni(III) (4, 7) and Ni(IV) (6c, 8)) intermediates were identified spectroscopically. In contrast to organometallic Ni(IV) complexes, (8) the formation of Ni(III) and, more so, Ni(IV) oxido complexes, although inferred, is controversial due to the implications of the oxo-wall premise. (9) Nevertheless, several Ni(II) and Ni(III) oxido or peroxido complexes, formed with O2 and H2O2, have been characterized already at low temperature. (24-27)
Here we show that a novel room-temperature-stable dinuclear Ni(IV) oxido complex (3), [(L)2Ni(IV)2(μ-O)3]2+ (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane), can be generated by reaction of the Ni(II) complexes (1, 2) with NaOCl (Scheme 1). The high oxidation state of 3 is stabilized by the tris-μ-oxido-bridged dinuclear structure. Furthermore, the reactivity of 3 toward direct C–H oxidation of organic substrates is demonstrated.

Scheme 1

Scheme 1. Formation of 3 from 1 and NaOCl
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Complex 3 is obtained within seconds of addition of near stoichiometric amounts of NaOCl to [(L)2Ni(II)2(μ-X)3]X·(H2O)n (where X = Cl (1) or Br (2), n = 5 or 7) (10) in methanol or acetonitrile at room temperature. The structure of 3 was elucidated through a combination of UV–vis absorption and resonance Raman spectroscopy and ESI mass spectrometry, supported by isotope labeling, crossover experiments, and DFT methods.

Results and Discussion

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Complexes 1 and 2 were prepared by methods analogous to those reported earlier (see SI for details). (10) The Raman spectra of 1 in the solid state (Figure S1) and in solution (i.e., methanol, acetonitrile, Figure S2) indicate that the complexes retain their structure; that is, the ligand (L) remains bound to Ni(II) upon dissolution. However, ESI mass spectrometry indicates that 1 can form mononuclear complexes with three (176.3 m/z: 4 [(L)Ni(II)(CH3CN)3)]2+) or two acetonitrile ligands (155.9 m/z: 5, ([(L)Ni(II)(CH3CN)2)]2+) by substitution of the chlorido ligands (Figure S3). Indeed, mixtures of 1 and 2 show rapid exchange of Cl– and Br– ligands (Figure S4). The 1H NMR spectrum of 1 in acetonitrile shows paramagnetically shifted and broadened signals at ca. 60, 90, and 120 ppm (Figure S5), and its UV–vis absorption spectrum in methanol and acetonitrile (Figure S6) shows bands at 384, 635, and 1014 nm. The DFT data (vide infra) indicate antiferromagnetically coupled Ni(II) ions in 1 and 2, consistent with observations by Wieghardt et al. (11) The C3h-symmetric DFT structure for both 1 and 2 is in excellent agreement with the X-ray structure, (11) with differences of ca. 0.01–0.02 Å between DFT and X-ray for Ni–N, Ni–Cl/Br, and Ni–Ni distances (Table S1). The antiferromagnetically coupled state lies lowest in energy (including COSMO solvation (12) and ZORA (13) relativistic effects, Table S2), (14, 15) in excellent agreement with experiment. (11) In this state, the locally spin-polarized triplet (S = 1) Ni(II) ions couple antiferromagnetically (AFM) to reach overall an open-shell singlet state. As a result, spin-up spin-density is observed around one Ni and spin-down around the other (Figure 1). This AFM state is only 0.3 kcal·mol–1 lower than the ferromagnetically (FM) coupled (S = 2) state (see SI section 7 for the corresponding spin-density plot). Both states would be consistent with the paramagnetic 1H NMR shifts (vide supra), but the AFM state is found to be slightly lower by both theory and experiment. The diamagnetic closed-shell singlet state, in which the Ni(II) ions are now locally in a closed-shell (S = 0) state, is higher in energy than the AFM state by 37.7 kcal·mol–1 (1) and 35.0 kcal·mol–1 (2). Finally, also an overall intermediate spin state (S = 1) was obtained, 25.5 kcal·mol–1 (1) and 23.4 kcal·mol–1 (2) higher in energy than the AFM state, where spin-density corresponding to the single occupation of an antibonding dx2–y2 orbital was observed on both Ni ions. Finally, the experimental NMR and UV–vis absorption spectra of the AFM state are similar to those of related Ni(II) complexes (Figure S7). (16)

Figure 1

Figure 1. Spin-density plot (S12g/TZ2P) for (antiferromagnetically coupled) 1 with spin-up spin-density shown in blue (around Nia, left) and spin-down spin-density in red (around Nib, right).

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Addition of NaOCl to 1 or 2 in methanol or in acetonitrile leads to a rapid increase in absorbance at 363 and 612 nm due to formation of 3 (Figure 1). In methanol, the visible absorption band decreases with a t1/2 of ca. 50 s at 20 °C (Figure S8), and the absorption spectrum after 20 min is similar to the initial spectrum, with only a minor shift from 388 to 378 nm (Figure 2). Notably, the rate of decay of 3 in methanol was substantially lower than the rate of the direct reaction of NaOCl with methanol in the absence of 1 (Figure S8), indicating that the formation of 3 competes with oxidation of methanol by NaOCl and that 3 is less reactive in the oxidation of methanol than NaOCl.

Figure 2

Figure 2. UV–vis absorption spectrum of 1 (3.5 mM) in methanol before (black) and after (red 6 s, blue 48 s, green 463 s) addition of 11 equiv of NaOCl(aq) at 293 K. Inset: Expansion of the NIR region. The data indicate that for 3 ε612 nm > 715 M–1·cm–1.

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In both the presence and absence of 1, near-quantitative (cf. NaOCl) oxidation of methanol to formaldehyde occurs (1.5:1, Figure S9), indicating that although at least 2 equiv of NaOCl are consumed in forming 3 from 1, these oxidation equivalents are still available for subsequent oxidation of methanol. Further additions of NaOCl in the presence of 1 resulted in the reappearance of the 612 nm absorption (Figure S10), confirming the integrity of the catalyst under reaction conditions. Similar changes were observed with NaOBr (Figure S11), which indicates that the same intermediate is formed with both oxidants (vide infra). Addition of H2O2 or purging with O2 (Figures S12 and S13) did not result in the appearance of 3.
Intermediate 3 forms upon addition of NaOCl to 1 also in acetonitrile (absorbance band at 612 nm), but persists for a substantially longer time period than in methanol, with a t1/2 of ca. 10 min at 20 °C and over 6 h at −15 °C (Figures S14 and S15), enabling characterization by resonance Raman spectroscopy, XANES, XES, and ESI mass spectrometry and reactivity with other substrates to be studied (vide infra). The maximum transient absorbance at 612 nm was obtained with 3–4 equiv of NaOCl (Figure S16) and is accompanied by an increase in oxidation state as confirmed by XANES and XES (Figure 3 and Figure S17).

Figure 3

Figure 3. (Top) Ni K XANES before (blue) and after (yellow) addition of 4 equiv of NaOCl to 1 (30 mM) in acetonitrile. (Bottom) Ni K edge XANES for structures 1, 3, and 3a, simulated using FEFF9.0 (18) using coordinates available from DFT-optimized structures (see the SI).

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The Ni K edge X-ray absorption near edge structure (XANES) as well as the X-ray emission (XES) spectra were recorded for 1 (30 mM) in acetonitrile before and after addition of NaOCl. Spectra were acquired over 5 min after addition when the concentration of 3 (generated from 1) was substantial, although Ni(II) species are present also. The Ni K edge XANES spectra of both 1 and the mixture of species formed after addition of NaOCl show a nondescript edge, i.e., no significant pre- edge features, which indicates a near-octahedral, six-coordinated, geometry around the Ni center for all species present (consistent with the structures 1, 3, and 3a).
The edge position is a function of the ligands present and geometry as well as oxidation state, and hence a direct conclusion based on XANES alone cannot be drawn. For example, for purely oxidic Ni systems, an energy shift of about 1.8 eV per oxidation state is reported, with a much lower shift for sulfur-based systems. (17) A conclusive statement as to the oxidation state requires the availability of a series of reference compounds with similar ligands and geometries (data for closely related structures are not yet available in the literature).
The energy shift of about 2 eV observed in the experimental spectra is consistent with an increase in oxidation state, but it will also reflect the change from chlorido to oxido ligands. Furthermore, the mixture of species available (including Ni(II)) reduces the magnitude of the observed shift and complicates interpretation.
The simulated XANES for complexes 1, 3, and 3a are displayed in Figure 3. (18) All XANES spectra have only a pre-edge feature at low energy and an otherwise featureless edge, consistent with six-coordinated geometries. A clear difference in the spectra of the Ni(II) 1 of 5 eV with the Ni(III) 3a and Ni(IV) 3a species is calculated, i.e., upon oxidation and change of ligands from Cl to O. It is, however, also clear that XANES data will not allow for distinguishing the Ni(III) and Ni(IV) species, i.e., complexes 3 and 3a. Furthermore, the Ni K edge XANES of 1 undergoes only a few electronvolts shift in the presence of NaOCl and not the full 5 eV shift, as it is a mixture of Ni(II) and nickel in higher oxidation states, resulting in only an average shift, i.e., between 2 and 3 eV, reflecting an overall average increase in oxidation state. The XES data at the Kβ1,3 edge also display an overall shift of a few electronvolts; however, the emission lines are sensitive to both oxidation state and ligand type also.
The three broad signals in the 1H NMR spectrum of 1 in acetonitrile decrease upon addition of NaOCl, suggesting the formation of a diamagnetic species, and then recover concomitant with the increase and decrease in absorbance at 612 nm (Figure S18). Samples flash frozen to 77 K at any time, however, did not indicate the presence of a mononuclear Ni(III) species by X-band EPR spectroscopy.
Generation of 3 by electrochemical oxidation of 1 was explored also. The cyclic voltammetry of 1 shows irreversible redox waves at 1.52, 1.35, and 1.05 V and an irreversible redox wave at 0.58 V on the return cycle. At higher scan rates (up to 10 V s–1) the initial oxidation wave at 1.05 V shows some evidence of chemical reversibility; however, the shifts in Ip,a (which are corrected for IRu) indicate that the oxidation is electrochemically irreversible also (Figure S19). Addition of NaOCl to 1 results (after 2 min) in a shift in the oxidation wave to 1.16 V, indicative of ligand exchange, e.g., CH3CN replacing Cl–. It should be noted, however, that the redox chemistry of NaOCl, concentration polarization, and the likely complex series of dis- and comproportionation reactions between 1 and 3 preclude the observation of a redox wave assignable to 3. One hour after addition of NaOCl, a further shift is observed, indicating ligand exchange to form a Ni(II) complex similar to 4 (Figure S20). Notably the voltammetry and spectroelectrochemistry were not affected substantially by the addition of water and NaCl (i.e., at concentrations present under reaction conditions).
The spectroelectrochemistry of 1 in acetonitrile shows that oxidation at 1.2 V leads to essentially no change in the UV absorption (Figure S21a). On the second cycle the redox wave is shifted to >1.58 V; again relatively little change in absorbance is observed, and after reduction below 0.86 V only minor shifts in absorbance at ca. 300 nm are observed, consistent with ligand exchange (Figure S21b). Bulk electrolysis of 1 shows an increase in absorption at 344 nm; however, the EPR spectrum (X-band 77 K) of this sample was silent, and hence oxidation leads to ligand exchange to a Ni(II) complex with a more positive redox potential rather than formation of a Ni(III) or Ni(IV) complex.
Attempts to isolate 3 by flash precipitation with KPF6 yielded the mononuclear Ni(II) compound [(L)Ni(II)(CH3CN)3]2+ (4) instead, reported earlier by Tak et al. as the B(Ph)4– salt, (16) in which the chlorido ligands are replaced by acetonitrile ligands to form a mononuclear complex (see the SI and Scheme 2). Notably, addition of NaOCl to 4 in acetonitrile results in the same visible absorption spectrum as obtained with 1 (Figure S23), indicating that the formation of 3 is not dependent on the initial form of the LNi(II) complex (with Cl–/Br–/CH3CN) and is consistent with the rapid equilibration of these species in solution. Furthermore, addition of NaOCl (4–10 equiv) to a 1:1 mixture of NiCl2 and the ligand (L) in acetonitrile results in the appearance of the bands at λmax 363 and 612 nm (Figure S24), consistent with a maximum 50% conversion to 3. In the absence of ligand (i.e., only NiCl2·6H2O) the band at 612 nm was not observed (Figure S25).

Scheme 2

Scheme 2. Formation of 3 from 1 and NaOCl and Subsequent Decay to 4 in Acetonitrile
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In earlier reports, (6) the presence of acetic acid was necessary for the formation of high-valent nickel complexes with NaOCl. Addition of acetic acid (4.5 equiv) to 3 in acetonitrile (generated by addition of 4.5 equiv of NaOCl to 1 (0.9 mM)) did not affect the absorbance at 612 nm significantly (Figure S26a). In contrast, addition of acetic acid (4.5 equiv) prior to addition of NaOCl to 1 (0.9 mM) precluded the appearance of the 612 nm band and hence formation of 3 (Figure S26b). (19)
The ESI mass spectra of 1 in acetonitrile show signals (m/z) assignable to [Ni(II)(L)(CH3CN)2]2+ (155.9 m/z), [Ni(II)(L)(CH3CN)3]2+ (176.3 m/z), [Ni(II)(L) (Cl)]+ (264.1 m/z), and [Ni(II)2(L)2(Cl)3]+ (565.2 m/z) (Figure S27). The spectrum obtained from a solution containing 3 shows an additional strong signal at 253.3 m/z with an isotope distribution consistent with two Ni centers (Figure S28), regardless of whether it was generated with NaOBr or NaOCl and with 2 in place of 1 (Figures S29–S33). Notably, however, the signal increased by 3 m/z units with Na18OCl (Figure S31). The m/z signal at 253.3 is therefore consistent with structures such as the peroxy-bridged 3a, (20) [(L)2Ni(III)2(μ-O)(μ-O-O)]2+, the mono-μ-oxo-bis-terminal-oxo 3b, [(L)-(O)═Ni(IV)-O-Ni(IV)═(O)-L]2+, and the tri-μ-oxido-bridged 3, [((L)2Ni(IV)2(μ-O)3]2+ (Scheme 3), with the latter structure 3 favored on the basis of Raman spectroscopy (vide infra) and DFT. (21)

Scheme 3

Scheme 3. Structures (3, 3a, 3b) Consistent with ESI Mass Spectral Data and Calculated Driving Forces for Their Formation from 1
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All possible spin states were explored by DFT methods for 3, 3a, and 3b. As expected for the d6 Ni(IV) ions in 3, the lowest energy (15) state corresponds to locally closed-shell singlet (S = 0) Ni(IV) ions. For consistency, we explored the possibility of other spin states and found several higher lying spin states, where, for example, the Ni(IV) ions had locally a triplet (S = 1) state that coupled to form overall a quintet (S = 2) state. However, these other spin states are >27 kcal·mol–1 higher in energy (see Table S2) and will not be discussed any further. For the d7 Ni(III) ions in 3a, the lowest energy (15) state corresponds to a doublet on each of the metals, which can be FM (S = 1) or AFM (open-shell singlet) coupled. The latter open-shell singlet state is lower in (Gibbs free) energy than the triplet by 2.1 kcal·mol–1, and 5.1 kcal·mol–1 lower than the diamagnetic closed-shell singlet state. All other spin states for 3a are >10 kcal·mol–1 higher in (Gibbs free) energy. The lowest energy for the d6 Ni(IV) ions in 3b corresponds to an AFM state, where each of the Ni(IV) ions is found locally in a triplet (S = 1) state. The AFM state is lower than the FM state in 3b by 1.2 kcal·mol–1, with the other spin states higher in energy by >10 kcal·mol–1.
The geometrical parameters for compound 3, which although isostructural to [(L)2Mn(IV)2(μ-O)3]2+, (22) are found to be somewhat different. The most prominent feature in [(L)2Mn(IV)2(μ-O)3]2+ is a short Mn(IV)–Mn(IV) distance of 2.30 Å, which is absent in 3, where the Ni(IV)–Ni(IV) is instead 2.46 Å; the latter distance is more similar to the bis-μ-oxo variant [L2MnIV2(O)2(μ-O)2] (2.62 Å). (22) Furthermore, the NiIV–N distance of 2.02 Å in 3 is substantially shorter than in [(L)2Mn(IV)2(μ-O)3]2+ (2.11 Å). The NiIV–(μ-O) distance in 3 of 1.85 Å is however similar to that in the MnIV analogue (1.82 Å). Overall, the DFT structure for 3 and the X-ray structure for [(L)2Mn(IV)2(μ-O)3]2+ are similar, which is apparent when superimposed (Figure S34).

Figure 4

Figure 4. Raman spectra (λexc 532 nm) of 1 (3.5 mM) in acetonitrile (a) and with (b) 4.5 equiv of NaOBr, (c) 4.5 equiv of Na16OCl, and (d) 4.5 equiv of Na18OCl. *Solvent band. #Raman band from quartz.

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The Raman spectrum of 3, with excitation resonant with the visible absorption band, shows enhanced Raman scattering at 801, 631, and 521 cm–1 (Figure 3), with only the band at 631 cm–1 (Δ[18O] = 32 cm–1) affected by the use of Na18OCl. The bands are unaffected by use of OBr– in place of OCl–. The DFT-calculated Raman spectrum for [(L)2Ni(IV)2(μ-16/18O)3]2+ (3) shows a penta-atomic symmetric stretching Ni–(O)3–Ni mode at 638 cm–1, which shifted to 609 cm–1 upon isotope labeling (i.e., Δ[18O] = 29 cm–1, Figure S35). Mixed labeling (i.e., varying ratios of 16O and 18O) experiments show the series of four bands expected for the four isotopologues and correspond well with the DFT-calculated shifts (Figure 5).

Figure 5

Figure 5. Top: Calculated spectra for 3 with various degrees of 18O substitution (16O3 (blue), 16O218O (red), 16O18O2 (green), 18O3 (purple)). Bottom: Resonance Raman spectra of 3 generated from 1 (4 mM) in methanol by addition of 4 equiv of NaOCl/H2O with (blue) 100% 16O, (red) 50% 18O, (green) 34% 18O, and (purple) 26% 18O.

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The band at 801 cm–1 corresponds to a symmetric Ni–N stretching (calcd by DFT at 782 cm–1, at the same position upon 18O labeling), while the band at 521 cm–1 involves mainly a combination of Ni–N and Ni–O stretching (calcd by DFT at 517 cm–1 and at 516 cm–1 upon 18O labeling). All of the vibrations of the normal modes are available in the SI. The modes observed for 3 are similar in energy to those of the isostructural complex [(L)2Mn(IV)2(μ-O)3]2+, which shows a Mn–(O)3–Mn stretch at 701 cm–1 (Δ18O = 33 cm–1). (23) Furthermore, the spectrum is similar to that reported by Riordan and co-workers for [((PhTttBu)Ni(III))2(μ-O)2], with a band at 585 cm–1 (Δ[18O] = 30 cm–1), (24) and by Fukuzumi and co-workers for [(L′Ni(III))2(μ-O)2]2+, where L′ = N,N-bis[2-(2-pyridyl)ethyl]-2-phenylethylamine, with a band at 612 cm–1 (Δ[18O] = 32 cm–1). (25) The higher Raman shift for 3 is consistent with an increase in the oxidation state from III to IV.
The Ni–O–O–Ni stretching modes in 3a are expected at higher wavenumbers compared to Ni–O–Ni modes; see, for example, the O–O stretch vibrations reported by Riordan and co-workers ([(Ni(tmc))2(μ-O-O)] at 778 cm–1; Δ[18O] = 43 cm–1) (26) and Gade and co-workers ([(Ni(iso-pmbox))2(μ-O-O)] at 742 cm–1; Δ[18O] = 36 cm–1). (27) This conclusion is supported by the DFT-calculated IR spectrum for 3a (Figure S36), which shows an O–O stretching band (Δ[18O] in parentheses) at 892 (841) cm–1, a Ni–N stretching mode at 768 (768) cm–1, and Ni–O bending/stretching modes at 663 (633), 601 (594), 585 (571), and 536 (516) cm–1. Of these modes, the 663 and 768 cm–1 modes are strongly IR active. Therefore, given that in the present system only the band at 631 cm–1 is affected by the use of 18OCl– and that the DFT-calculated IR spectrum of 3a (Figure S36) indicates bands at ca. 660 and 770 cm–1 only and not a band at ca. 801 cm–1, the peroxy species can be discarded. The same is true for 3b, which shows terminal-oxo Ni–O stretches at 742 cm–1 (shifting to 718 cm–1 upon 18O labeling, i.e., Δ18O = 24 cm–1), 700 cm–1 (Δ18O = 28 cm–1), and 689 cm–1 (Δ18O = 26 cm–1); the Ni–(μ-O)–Ni stretch is found at 653 cm–1 (Δ18O = 17 cm–1). No bands are observed around 521 cm–1, and all bands show significant isotope effects. Therefore, although the ESI mass spectral data could correspond also to a peroxy-bridged (3a) or the mono-μ-oxo species (3b), the most appropriate structural assignment for the high-valent nickel species is 3 based on the vibrational spectra.
DFT calculations provide further support for this assignment in the thermochemistry of the reaction of 1 and 2 with NaOCl to form 3. Mass spectral data indicate that the reactive intermediate 3 has the composition [(L)2Ni2O3]2+, and the absence of EPR (X-band) signals at 77 K at any time suggests that mononuclear Ni(III) complexes are not present to a significant extent. Hence, geometry optimizations were performed with all spin multiplicities for 1, 2, 3, and 3a, as well as possible mononuclear Ni(II) complexes, e.g., [(L)Ni(II)(CH3CN)3]2+ (4) and [(L)Ni(II) (CH3CN)2]2+ (5) (Table S2). Antiferromagnetically coupled dinuclear species were found as lowest energy for 1, 2, 3a, and 3b, while a closed-shell spin state was found for 3 (vide supra); a high-spin Ni(II) (S = 1) ground state was found for 4 and 5. The reactions of 1 with NaOCl to form 3, 3a, or 3b (Scheme 3) were calculated to be exergonic by −92.5, −88.1, and −50.3 kcal·mol–1, respectively; hence, 3 is 4.46 kcal·mol–1 more stable than 3a and 42.2 kcal·mol–1 than 3b, in terms of Gibbs energy (in electronic energy: 7.50 and 46.11 kcal·mol–1, respectively for 3a and 3b), Table S3.
Further spectroscopic evidence for the formation of 3, and not 3a or 3b, is obtained by mixed labeling experiments. In these experiments we applied ratios of pure 16O (3:0), pure 18O (0:3), and 1:2/2:1 mixtures of these, such that we would have four different distributions with on average the incorporation of 0, 1, 2, and 3 labeled oxygens into the complex. The observed isotope shifts observed in our Raman spectra with these mixed labeling experiments match perfectly with the corresponding DFT isotope shifts; that is, the 631 cm–1 peak (638 cm–1 DFT) shifts to 623 cm–1 (630 cm–1 DFT), to 613 cm–1 (622 cm–1 DFT), and finally to 599 (609 cm–1 DFT).
Overall, the spectroscopic and computational data are consistent with the assignment of the intermediate as 3 ([(L)2Ni(IV)2(μ-16O)3]2+). The mechanism by which 3 forms from Ni(II) complexes undoubtedly involves multiple elementary steps. However, the coordination of OCl– to Ni(II) is expected to be facile given the rapid exchange of Cl–, Br–, and CH3CN ligands. Heterolytic cleavage of Ni(II)–O–Cl to form a transient intermediate Ni(IV) species and Cl– is presumably followed by formation of a (μ-O)3-bridged Ni(IV) dimer, which does not show antiferromagnetic coupling, in contrast with the equivalent manganese complex, but instead corresponds to diamagnetic closed-shell Ni(IV) ions.
Finally, although 3 undergoes rapid self-decay in methanol to yield formaldehyde, in acetonitrile it is relatively stable, allowing for its reactivity with organic substrates to be assessed. The addition of ca. 4 equiv of substrate (e.g., xanthene, 9,10-dihydroanthracene, and fluorene) resulted in a complete loss of absorbance at 612 nm within ca. 6 min (70, 150, and 350 s, respectively, Figure S37). At −15 °C, 3 is stable for over 6 h (Figure S38),; however, addition of 4 equiv of xanthene resulted in a rapid loss in absorbance at 612 nm (within ca. 275 s, Figure S39). Addition of 50 equiv of fluorene to 3 resulted in the disappearance of the signal at m/z 253.3 and a recovery of the signals of 1 and 4 (Figure S40). Hence, although substrates react directly with NaOCl, 3 engages in C–H oxidation also (Figure S39).

Conclusions

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Complex 3 represents the first example of a Ni(IV)-oxido-bridged dimer. Its generation from NaOCl and subsequent reaction with organic substrates opens up the possibility to use NaOCl as a terminal oxidant. The intermediacy of a transition metal catalyst opens the possibility of engaging in selective oxidations, thereby taming the reactivity of this potent oxidant.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b04158.

  • Animated gifs for selected vibrational modes between 517 and 893 cm−1 of 3 (ZIP)

  • Animated gifs for selected vibrational modes between 536 and 892 cm−1 of 3a (ZIP)

  • Animated gifs for vibrational modes at 653, 689, 700, 742 cm−1 of 3b (ZIP)

  • Details of synthesis and charcaterization of complexes 1, 2, and 4, UV–vis absorption, (resonance) Raman, NMR, EPR spectroscopy, ESI-MS, XANES, XES, and computational data (PDF)

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Author Information

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  • Corresponding Authors
  • Authors
    • Sandeep K. Padamati - Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands
    • Davide Angelone - Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands;  IQCC & Departament de Química, Universitat de Girona, Campus Montilivi (Ciències), 17003 Girona, Spain
    • Apparao Draksharapu - Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands
    • Gloria Primi - Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands
    • David J. Martin - Sustainable Materials Characterisation, Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands;  Orcidhttp://orcid.org/0000-0002-3549-4202
    • Moniek Tromp - Sustainable Materials Characterisation, Van’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

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The Ubbo Emmius fund of the University of Groningen, the European Research Council (StG, no. 279549, W.R.B.), NWO for a VIDI grant (723.014.010, D.J.M. and M.T.), The Netherlands Ministry of Education, Culture and Science (Gravity program 024.001.035, W.R.B.), MINECO (CTQ2014-59212-P and CTQ2015-70851-ERC, M.S.), GenCat (2014SGR1202, M.S.), FEDER (UNGI10-4E-801, M.S.), and COST action CM1305 “ECOSTBio” (W.R.B., COST-STSM-CM1305-29045) are acknowledged for financial support. A. van Dam (ERIBA) is thanked for assistance with mass spectrometry.

References

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This article references 27 other publications.

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  • Abstract

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    Scheme 1

    Scheme 1. Formation of 3 from 1 and NaOCl
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    Figure 1

    Figure 1. Spin-density plot (S12g/TZ2P) for (antiferromagnetically coupled) 1 with spin-up spin-density shown in blue (around Nia, left) and spin-down spin-density in red (around Nib, right).

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    Figure 2

    Figure 2. UV–vis absorption spectrum of 1 (3.5 mM) in methanol before (black) and after (red 6 s, blue 48 s, green 463 s) addition of 11 equiv of NaOCl(aq) at 293 K. Inset: Expansion of the NIR region. The data indicate that for 3 ε612 nm > 715 M–1·cm–1.

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    Figure 3

    Figure 3. (Top) Ni K XANES before (blue) and after (yellow) addition of 4 equiv of NaOCl to 1 (30 mM) in acetonitrile. (Bottom) Ni K edge XANES for structures 1, 3, and 3a, simulated using FEFF9.0 (18) using coordinates available from DFT-optimized structures (see the SI).

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    Scheme 2

    Scheme 2. Formation of 3 from 1 and NaOCl and Subsequent Decay to 4 in Acetonitrile
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    Scheme 3

    Scheme 3. Structures (3, 3a, 3b) Consistent with ESI Mass Spectral Data and Calculated Driving Forces for Their Formation from 1
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    Figure 4

    Figure 4. Raman spectra (λexc 532 nm) of 1 (3.5 mM) in acetonitrile (a) and with (b) 4.5 equiv of NaOBr, (c) 4.5 equiv of Na16OCl, and (d) 4.5 equiv of Na18OCl. *Solvent band. #Raman band from quartz.

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    Figure 5

    Figure 5. Top: Calculated spectra for 3 with various degrees of 18O substitution (16O3 (blue), 16O218O (red), 16O18O2 (green), 18O3 (purple)). Bottom: Resonance Raman spectra of 3 generated from 1 (4 mM) in methanol by addition of 4 equiv of NaOCl/H2O with (blue) 100% 16O, (red) 50% 18O, (green) 34% 18O, and (purple) 26% 18O.

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      Current Opinion in Chemical Biology (2005), 9 (2), 152-163CODEN: COCBF4; ISSN:1367-5931. (Elsevier Ltd.)
      A review and discussion. Enzymes contg. heme, non-heme Fe, and Cu active sites play important roles in the activation of O2 for substrate oxidn. One key reaction step is C-H bond cleavage through H-atom abstraction. On the basis of the ligand environment and the redox properties of the metal, these enzymes employ different methods of O2 activation. Heme enzymes are able to stabilize the very reactive Fe(IV)-oxo porphyrin-radical intermediate. This is generally not accessible for non-heme Fe systems, which can instead use low-spin ferric-hydroperoxo and Fe(IV)-oxo species as reactive oxidants. Cu enzymes employ still a different strategy and achieve H-atom abstraction potentially through a superoxo intermediate. This review compares and contrasts the electronic structures and reactivities of these various O intermediates.
      (b) Bertini, I.; Gray, H. B.; Stiefel, E. I.; Valentine, J. S. Biological.Inorganic Chemistry. Structure & Reactivity; University Science Books: Sausalito, CA, 2007.
      There is no corresponding record for this reference.
      (c) Meunier, B. Chem. Rev. 1992, 92, 1411– 1456 DOI: 10.1021/cr00014a008
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      (d) Nam, W. Acc. Chem. Res. 2015, 48, 2415– 2423 DOI: 10.1021/acs.accounts.5b00218
      2d
      Synthetic Mononuclear Nonheme Iron-Oxygen Intermediates
      Nam, Wonwoo
      Accounts of Chemical Research (2015), 48 (8), 2415-2423CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)
      A review. Mononuclear nonheme iron-oxygen species, such as iron-superoxo, -peroxo, -hydroperoxo, and -oxo, are key intermediates involved in dioxygen activation and oxidn. reactions catalyzed by nonheme iron enzymes. Because these iron-oxygen intermediates are short-lived due to their thermal instability and high reactivity, it is challenging to study their structural and spectroscopic properties and reactivity in the catalytic cycles of the enzymic reactions themselves. One way to approach such problems is to synthesize biomimetic iron-oxygen complexes and to tune their geometric and electronic structures for structural characterization and reactivity studies. Indeed, a no. of biol. important iron-oxygen species, such as mononuclear nonheme iron(III)-superoxo, iron(III)-peroxo, iron(III)-hydroperoxo, iron(IV)-oxo, and iron(V)-oxo complexes, were synthesized recently, and the 1st x-ray crystal structures of iron(III)-superoxo, iron(III)-peroxo, and iron(IV)-oxo complexes in nonheme iron models were successfully obtained. Thus, the authors' understanding of iron-oxygen intermediates in biol. reactions was aided greatly from the studies of the structural and spectroscopic properties and the reactivities of the synthetic biomimetic analogs. In this Account, the authors describe the authors' recent results on the synthesis and characterization of mononuclear nonheme iron-oxygen complexes bearing simple macrocyclic ligands, such as N-tetramethylated cyclam ligand (TMC) and tetraamido macrocyclic ligand (TAML). In the case of iron-superoxo complexes, an iron(III)-superoxo complex, [(TAML)FeIII(O2)]2-, is described, including its crystal structure and reactivities in electrophilic and nucleophilic oxidative reactions, and its properties are compared with those of a chromium(III)-superoxo complex, [(TMC)CrIII(O2)(Cl)]+, with respect to its reactivities in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions. In the case of iron-peroxo intermediates, an x-ray crystal structure of an iron(III)-peroxo complex binding the peroxo ligand in a side-on (η2) fashion, [(TMC)FeIII(O2)]+, is described. Iron(III)-peroxo complexes binding redox-inactive metal ions are described and discussed in light of the role of redox-inactive metal ions in O-O bond activation in cytochrome c oxidase and O2-evolution in photosystem II. In the case of iron-hydroperoxo intermediates, mononuclear nonheme iron(III)-hydroperoxo complexes can be generated upon protonation of iron(III)-peroxo complexes or by hydrogen atom abstraction (HAA) of hydrocarbon C-H bonds by iron(III)-superoxo complexes. Reactivities of the iron(III)-hydroperoxo complexes in both electrophilic and nucleophilic oxidative reactions are described along with a discussion of O-O bond cleavage mechanisms. In the last section of this Account, a brief summary is presented of developments in mononuclear nonheme iron(IV)-oxo complexes since the 1st structurally characterized iron(IV)-oxo complex, [(TMC)FeIV(O)]2+, is reported. Although the field of nonheme iron-oxygen intermediates (e.g., Fe-O2, Fe-O2H, and Fe-O) was developed greatly through intense synthetic, structural, spectroscopic, reactivity, and theor. studies in the communities of bio inorg. and biomimetic chem. over the past 10 years, there is still much to be explored in trapping, characterizing, and understanding the chem. properties of the key iron-oxygen intermediates involved in dioxygen activation and oxidn. reactions by nonheme iron enzymes and their biomimetic compds.
      (e) Oloo, W. N.; Que, L. Acc. Chem. Res. 2015, 48, 2612– 2621 DOI: 10.1021/acs.accounts.5b00053
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    3. 3
      Shearer, J. Acc. Chem. Res. 2014, 47, 2332– 2341 DOI: 10.1021/ar500060s
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    4. 4
      (a) Cho, J.; Kang, Y.; Liu, L. V.; Sarangi, R.; Solomon, E. I.; Nam, W. Chem. Sci. 2013, 4, 1502– 1508 DOI: 10.1039/c3sc22173c
      4a
      Mononuclear nickel(II)-superoxo and nickel(III)-peroxo complexes bearing a common macrocyclic TMC ligand
      Cho, Jaeheung; Kang, Hye Yeon; Liu, Lei V.; Sarangi, Ritimukta; Solomon, Edward I.; Nam, Wonwoo
      Chemical Science (2013), 4 (4), 1502-1508CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Mononuclear metal-dioxygen adducts, such as metal-superoxo and -peroxo species, were generated as key intermediates in the catalytic cycles of dioxygen activation by heme and non-heme metalloenzymes. The authors showed recently that the geometric and electronic structure of the Ni-O2 core in [Ni(n-TMC)(O2)]+ (n = 12 and 14) varies depending on the ring size of the supporting TMC ligand. Mononuclear Ni(II)-superoxo and Ni(III)-peroxo complexes bearing a common macrocyclic 13-TMC ligand, such as [NiII(13-TMC)(O2)]+ and [NiIII(13-TMC)(O2)]+, were synthesized in the reaction of [NiII(13-TMC)(MeCN)]2+ and H2O2 in the presence of tetramethylammonium hydroxide (TMAH) and triethylamine (TEA), resp. The Ni(II)-superoxo and Ni(III)-peroxo complexes bearing the common 13-TMC ligand were successfully characterized by various spectroscopic methods, x-ray crystallog. and DFT calcns. Based on the combined exptl. and theor. studies, the superoxo ligand in [NiII(13-TMC)(O2)]+ is bound in an end-on fashion to the nickel(II) center, whereas the peroxo ligand in [NiIII(13-TMC)(O2)]+ is bound in a side-on fashion to the nickel(III) center. Reactivity studies performed with the Ni(II)-superoxo and Ni(III)-peroxo complexes toward org. substrates reveal that the former possesses an electrophilic character, whereas the latter is an active oxidant in nucleophilic reaction.
      (b) Honda, K.; Cho, J.; Matsumoto, T.; Roh, J.; Furutachi, H.; Tosha, T.; Kubo, M.; Fujinami, S.; Ogura, T.; Kitagawa, T.; Suzuki, M. Angew. Chem., Int. Ed. 2009, 48, 3304– 3307 DOI: 10.1002/anie.200900222
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      (c) Tano, T.; Doi, Y.; Inosako, M.; Kunishita, A.; Kubo, M.; Ishimaru, H.; Ogura, T.; Sugimoto, H.; Itoh, S. Bull. Chem. Soc. Jpn. 2010, 83, 530– 538 DOI: 10.1246/bcsj.20090346
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      (d) Kunishita, A.; Doi, Y.; Kubo, M.; Ogura, T.; Sugimoto, H.; Itoh, S. Inorg. Chem. 2009, 48, 4997– 5004 DOI: 10.1021/ic900059m
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      (e) Morimoto, Y.; Bunno, S.; Fujieda, N.; Sugimoto, H.; Itoh, S. J. Am. Chem. Soc. 2015, 137, 5867– 5870 DOI: 10.1021/jacs.5b01814
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    5. 5
      (a) Corona, T.; Pfaff, F. F.; Acua-Pares, F.; Draksharapu, A.; Whiteoak, C. J.; Martin-Diaconescu, V.; Lloret-Fillol, J.; Browne, W. R.; Ray, K.; Company, A. Chem. - Eur. J. 2015, 21, 15029– 15038 DOI: 10.1002/chem.201501841
      5a
      Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species
      Corona, Teresa; Pfaff, Florian F.; Acuna-Pares, Ferran; Draksharapu, Apparao; Whiteoak, Christopher J.; Martin-Diaconescu, Vlad; Lloret-Fillol, Julio; Browne, Wesley R.; Ray, Kallol; Company, Anna
      Chemistry - A European Journal (2015), 21 (42), 15029-15038CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a NiII precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compd. is only detectable at temps. below 250 K and is much more reactive toward org. substrates (i.e., C-H bonds, C-C bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic O-O bond cleavage of a Ni-HmCPBA precursor, which is concluded from exptl. and computational data. On the basis of spectroscopy and DFT calcns., this reactive species is proposed to be a NiIII-oxyl compd.
      (b) Pfaff, F. F.; Heims, F.; Kundu, S.; Mebs, S.; Ray, K. Chem. Commun. 2012, 48, 3730– 3732 DOI: 10.1039/c2cc30716b
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    6. 6
      (a) Draksharapu, A.; Codolá, Z.; Gómez, L.; Lloret-Fillol, J.; Browne, W. R.; Costas, M. Inorg. Chem. 2015, 54, 10656– 10666 DOI: 10.1021/acs.inorgchem.5b01463
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      (b) Pirovano, P.; Farquhar, E. R.; Swart, M.; McDonald, A. R. J. Am. Chem. Soc. 2016, 138, 14362– 14370 DOI: 10.1021/jacs.6b08406
      There is no corresponding record for this reference.
      (c) Corona, T.; Draksharapu, A.; Padamati, S. K.; Gamba, I.; Martin-Diaconescu, V.; Acuña-Parés, F.; Browne, W. R.; Company, A. J. Am. Chem. Soc. 2016, 138, 12987– 12996 DOI: 10.1021/jacs.6b07544
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    7. 7
      Corona, T.; Company, A. Chem. - Eur. J. 2016, 22, 13422– 13429 DOI: 10.1002/chem.201602414
      7
      Spectroscopically Characterized Synthetic Mononuclear Nickel-Oxygen Species
      Corona, Teresa; Company, Anna
      Chemistry - A European Journal (2016), 22 (38), 13422-13429CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review; iron, copper, and manganese are the predominant metals found in oxygenases that perform efficient and selective hydrocarbon oxidns. and for this reason, a large no. of the corresponding metal-oxygen species has been described. However, in recent years nickel has been found in the active site of enzymes involved in oxidn. processes, in which nickel-dioxygen species are proposed to play a key role. Owing to this biol. relevance and to the existence of different catalytic protocols that involve the use of nickel catalysts in oxidn. reactions, there is a growing interest in the detection and characterization of nickel-oxygen species relevant to these processes. In this Minireview the spectroscopically/structurally characterized synthetic superoxo, peroxo, and oxonickel species that have been reported to date are described. From these studies it becomes clear that nickel is a very promising metal in the field of oxidn. chem. with still unexplored possibilities.
    8. 8
      (a) Camasso, N. M.; Sanford, M. S. Science 2015, 347, 1– 7 DOI: 10.1126/science.aaa4526
      There is no corresponding record for this reference.
      (b) Riordan, C. G. Science 2015, 347, 1203 DOI: 10.1126/science.aaa7553
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    9. 9
      (a) Gray, H. B.; Hare, C. R. Inorg. Chem. 1962, 1, 363– 368 DOI: 10.1021/ic50002a034
      There is no corresponding record for this reference.
      (b) O’Halloran, K. P.; Zhao, C.; Ando, N. S.; Schultz, A. J.; Koetzle, T. F.; Piccoli, P. M. B.; Hedman, B.; Hodgson, K. O.; Bobyr, E.; Kirk, M. L.; Knottenbelt, S.; Depperman, E. C.; Stein, B.; Anderson, T. M.; Cao, R.; Geletii, Y. V.; Hardcastle, K. I.; Musaev, D. G.; Neiwert, W. A.; Fang, X.; Morokuma, K.; Wu, S.; Kögerler, P.; Hill, C. L. Inorg. Chem. 2012, 51, 7025– 7031 DOI: 10.1021/ic2008914
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    10. 10
      Wieghardt, K.; Schmidt, W.; Herrmann, W.; Kueppers, H. J. Inorg. Chem. 1983, 22, 2953– 2956 DOI: 10.1021/ic00162a037
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    11. 11
      Bossek, U.; Nühlen, D.; Bill, E.; Glaser, T.; Krebs, C.; Weyhermüller, T.; Wieghardt, K.; Lengen, M.; Trautwein, A. X. Inorg. Chem. 1997, 36, 2834– 2843 DOI: 10.1021/ic970119h
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    12. 12
      (a) Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkin Trans. 2 1993, 799– 805 DOI: 10.1039/P29930000799
      12a
      COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
      Klamt, A.; Schueuermann, G.
      Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999) (1993), (5), 799-805CODEN: JCPKBH; ISSN:0300-9580.
      Starting from the screening in conductors, an algorithm for the accurate calcn. of dielec. screening effects in solvents is presented, which leads to rather simple explicit expressions for the screening energy and its analytic gradient with respect to the solute coordinates. Thus geometry optimization of a solute within a realistic dielec. continuum model becomes practicable for the first time. The algorithm is suited for mol. mechanics as well as for any MO algorithm. The implementation into MOPAC and some example applications are reported.
      (b) Pye, C. C.; Ziegler, T. Theor. Chem. Acc. 1999, 101, 396– 408 DOI: 10.1007/s002140050457
      12b
      An implementation of the conductor-like screening model of solvation within the Amsterdam density functional package
      Pye, Cory C.; Ziegler, Tom
      Theoretical Chemistry Accounts (1999), 101 (6), 396-408CODEN: TCACFW; ISSN:1432-881X. (Springer-Verlag)
      The conductor-like screening model (COSMO) of solvation was implemented in the Amsterdam d. functional program with max. flexibility in mind. Four cavity definitions were incorporated. Several iterative schemes were tested for solving the COSMO equations. The biconjugate gradient method proves to be both robust and memory-conserving. The interaction between the surface charges and the electron d. may be calcd. by integrating over either the fitted or exact d., or by calcg. the mol. potential. A disk-smearing algorithm is applied in the former case to avoid singularities. Several SCF/COSMO coupling schemes were examd. in an attempt to reduce computational effort. A gradient-preserving algorithm for removing outlying charge was implemented. Preliminary optimized radii are given. Applications to the benzene oxide-oxepin valence tautomerization and to glycine conformation are presented.
      (c) Swart, M.; Rösler, E.; Bickelhaupt, F. M. Eur. J. Inorg. Chem. 2007, 2007, 3646– 3654 DOI: 10.1002/ejic.200700228
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    13. 13
      van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, 4597– 4610 DOI: 10.1063/1.466059
      13
      Relativistic regular two-component Hamiltonians
      van Lenthe, E.; Baerends, E. J.; Snijders, J. G.
      Journal of Chemical Physics (1993), 99 (6), 4597-610CODEN: JCPSA6; ISSN:0021-9606.
      In the present work, potential-dependent transformations were used to transform the four-component Dirac Hamiltonian into relativistic, effective, two-component, regular Hamiltonians. To zeroth order, the expansions give second-order differential equations (just like the Schroedinger equation), which already contain the most important relativistic effects, including spin-orbit coupling. One of the zeroth- order Hamiltonians is identical to the one obtained earlier by Ch. Chang, et al., (1986). By using these Hamiltonians, self-consistent all-electron and frozen-core calcns., as well as first-order perturbation calcns. were done for the uranium atom. They gave very accurate results, esp. for the one-electron energies and electron densities of the valence orbitals.
    14. 14
      (a) Swart, M. Chem. Phys. Lett. 2013, 580, 166– 171 DOI: 10.1016/j.cplett.2013.06.045
      There is no corresponding record for this reference.
      (b) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098– 3100 DOI: 10.1103/PhysRevA.38.3098
      14b
      Density-functional exchange-energy approximation with correct asymptotic behavior
      Becke, A. D.
      Physical Review A: Atomic, Molecular, and Optical Physics (1988), 38 (6), 3098-100CODEN: PLRAAN; ISSN:0556-2791.
      Current gradient-cor. d.-functional approxns. for the exchange energies of at. and mol. systems fail to reproduce the correct 1/r asymptotic behavior of the exchange-energy d. A gradient-cor. exchange-energy functional is given with the proper asymptotic limit. This functional, contg. only one parameter, fits the exact Hartree-Fock exchange energies of a wide variety of at. systems with remarkable accuracy, surpassing the performance of previous functionals contg. two parameters or more.
      (c) Perdew, J. P. Phys. Rev. B: Condens. Matter Mater. Phys. 1986, 33, 8822– 8824 DOI: 10.1103/PhysRevB.33.8822
      14c
      Density-functional approximation for the correlation energy of the inhomogeneous electron gas
      Perdew
      Physical review. B, Condensed matter (1986), 33 (12), 8822-8824 ISSN:0163-1829.
      There is no expanded citation for this reference.
    15. 15

      At S12g/TZ2P//BP86-D3/TDZP.

      There is no corresponding record for this reference.
    16. 16
      Tak, H.; Lee, H.; Kang, J.; Cho, J. Inorg. Chem. Front. 2016, 3, 157– 163 DOI: 10.1039/C5QI00206K
      16
      A high-spin nickel(II) borohydride complex in dehalogenation
      Tak, Hyeonwoo; Lee, Hyunjoo; Kang, Joongoo; Cho, Jaeheung
      Inorganic Chemistry Frontiers (2016), 3 (1), 157-163CODEN: ICFNAW; ISSN:2052-1553. (Royal Society of Chemistry)
      A nickel(II)-borohydride complex bearing a macrocyclic tridentate N-donor ligand, [Ni(Me3-TACN)(BH4)(CH3CN)]+ (Me3-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane), was prepd., isolated, and characterized by various physicochem. methods, including UV-vis, ESI-MS, IR and X-ray analyses. The structural and spectroscopic characterization clearly shows that the borohydride ligand is bound to the high-spin nickel(II) center in an η2-manner. D. functional theory calcns. provided geometric information of 2, showing that the η2-binding of borohydride to the nickel center is more favorable than the η3-binding mode in CH3CN. The complex is paramagnetic with an effective magnetic moment of 2.9μB consistent with a d8 high-spin system. The reactivity of the high-spin nickel(II)-borohydride complex was examd. in dehalogenation with numerous halocarbons. A kinetic isotope effect value of 1.7 was obsd. in the dehalogenation of CHCl3 by the nickel(II)-borohydride complex. Kinetic studies and isotopic labeling expts. implicate that hydride ion or hydrogen atom transfer from the borohydride group is the rate detg. step. The pos. Hammett ρ value of 1.2, obtained in the reactions of [Ni(Me3-TACN)(BH4)(CH3CN)]+ and para-substituted benzoyl chloride, indicates that the dehalogenation by the nickel(II)-borohydride species occurs via a nucleophilic reaction.
    17. 17
      (a) Sun, Y.-K; Kim, M. G.; Kang, S. H.; Amine, K. J. Mater. Chem. 2003, 13, 319– 322 DOI: 10.1039/b209379k
      There is no corresponding record for this reference.
      (b) Gu, W.; Wang, H.; Wang, K. Dalton Trans. 2014, 43, 6406– 6413 DOI: 10.1039/c4dt00308j
      There is no corresponding record for this reference.
    18. 18
      Rehr, J. J.; Kas, J. J.; Vila, F. D.; Prange, M. P.; Jorissen, K. Phys. Chem. Chem. Phys. 2010, 12, 5503– 5513 DOI: 10.1039/b926434e
      18
      Parameter-free calculations of X-ray spectra with FEFF9
      Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.; Prange, Micah P.; Jorissen, Kevin
      Physical Chemistry Chemical Physics (2010), 12 (21), 5503-5513CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      A review. The authors briefly review implementation of the real-space Green's function (RSGF) approach for calcns. of x-ray spectra, focusing on recently developed parameter free models for dominant many-body effects. Although the RSGF approach was widely used both for near edge (XANES) and extended (EXAFS) ranges, previous implementations relied on semi-phenomenol. methods, e.g., the plasmon-pole model for the self-energy, the final-state rule for screened core hole effects, and the correlated Debye model for vibrational damping. Here the authors describe how these approxns. can be replaced by efficient ab initio models including a many-pole model of the self-energy, inelastic losses and multiple-electron excitations; a linear response approach for the core hole; and a Lanczos approach for Debye-Waller effects. The authors also discuss the implementation of these models and software improvements within the FEFF9 code, together with a no. of examples.
    19. 19

      In the absence of Ni(II) or 1, NaOCl is stable in CH3CN.

      There is no corresponding record for this reference.
    20. 20

      This complex is reminiscent of the (μ-η2:η2-disulfido)dinickel(II) complexes with 6-methyl-TPA ligands reported by Itoh et al.; see:

      Inosako, M.; Kunishita, A.; Kubo, M.; Ogura, T.; Sugimoto, T.; Itoh, S. Dalton Trans. 2009, 43, 9410– 9147 DOI: 10.1039/b910237j
      There is no corresponding record for this reference.
    21. 21

      The formation of species such as (O═Ni(IV)–O–Ni(IV)═O) is highly unlikely, as it is calculated to lie 45 to 58 kcal mol–1 (depending on functional used, e.g., BP86-D3 and S12g) higher in energy than even the peroxy species 3a. Furthermore, DFT calculations indicate a high tendency for a species to converge to the structure of the 3a species. In addition ligand hydroxylation can be discounted on the basis of the recovery of the Ni(II) complexes, e.g., 1 and 4, once 3 has reacted with solvent or substrate.

      There is no corresponding record for this reference.
    22. 22
      Wieghardt, K.; Bossek, U.; Nuber, B.; Weiss, J.; Bonvoisin, J.; Corbella, M.; Vitols, S. E.; Girerd, J. J. J. Am. Chem. Soc. 1988, 110, 7398– 7411 DOI: 10.1021/ja00230a021
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    23. 23
      (a) Hage, R.; Krijnen, B.; Warnaar, J. B.; Hartl, F.; Stufkens, D. J.; Snoeck, T. L. Inorg. Chem. 1995, 34, 4973– 4978 DOI: 10.1021/ic00124a010
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      (b) Angelone, D.; Abdolahzadeh, S.; de Boer, J. W.; Browne, W. R. Eur. J. Inorg. Chem. 2015, 21, 3532– 3542 DOI: 10.1002/ejic.201500195
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    24. 24
      Mandimutsira, B. S.; Yamarik, J. L.; Brunold, T. C.; Gu, W.; Cramer, S. P.; Riordan, C. G. J. Am. Chem. Soc. 2001, 123, 9194– 9195 DOI: 10.1021/ja016209+
      There is no corresponding record for this reference.

      PhTttBu = phenyltris((tert-butylthio)methyl)borate.

    25. 25
      Itoh, S.; Bandoh, H.; Nakagawa, M.; Nagatomo, S.; Kitagawa, T.; Karlin, K. D.; Fukuzumi, S. J. Am. Chem. Soc. 2001, 123, 11168– 11178 DOI: 10.1021/ja0104094
      There is no corresponding record for this reference.
    26. 26
      Kieber-Emmons, M. T.; Schenker, R.; Yap, G. P. A.; Brunold, T. C.; Riordan, C. G. Angew. Chem. 2004, 116, 6884– 6886 DOI: 10.1002/ange.200460747
      There is no corresponding record for this reference.

      tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazadodecane.

    27. 27
      Rettenmeier, C. A.; Wadepohl, H.; Gade, L. H. Angew. Chem., Int. Ed. 2015, 54, 4880– 4884 DOI: 10.1002/anie.201500141
      There is no corresponding record for this reference.

      iso-pmbox = bis(oxazolinylmethylidene)pyrrolidine.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b04158.

    • Animated gifs for selected vibrational modes between 517 and 893 cm−1 of 3 (ZIP)

    • Animated gifs for selected vibrational modes between 536 and 892 cm−1 of 3a (ZIP)

    • Animated gifs for vibrational modes at 653, 689, 700, 742 cm−1 of 3b (ZIP)

    • Details of synthesis and charcaterization of complexes 1, 2, and 4, UV–vis absorption, (resonance) Raman, NMR, EPR spectroscopy, ESI-MS, XANES, XES, and computational data (PDF)


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