A CoII-Hydroxide Complex That Converts Directly to a CoII-Acetamide during Catalytic Nitrile Hydration.

In exploring structural and functional mimics of nitrile hydratases, we report the synthesis of the pseudo-trigonal bipyramidal CoII complexes (K)[CoII(DMF)(LPh)] (1(DMF)), (NMe4)2[CoII(OAc)(LPh)] (1(OAc)), and (NMe4)2[CoII(OH)(LPh)] (1(OH)) (LPh = 2,2',2''-nitrilo-tris-(N-phenylacetamide; DMF = N,N-dimethylformamide; -OAc = acetate)). The complexes were characterized using NMR, FT-IR, ESI-MS, electronic absorption spectroscopy, and X-ray crystallography, showing the LPh ligand to bind in a tetradentate tripodal fashion alongside the respective ancillary donor. One of the complexes, 1(OH), is an unusual structural and functional mimic of the Co active site in Co nitrile hydratases. 1(OH) reacted with acetonitrile to yield the CoII-acetamide complex (NMe4)2[CoII(NHC(O)CH3)(LPh)], 2, which was also thoroughly characterized. In the presence of excess hydroxide, 1(OH) was found to catalyze quantitative conversion of the added hydroxide into acetamide. Despite the differences in Co oxidation state in nitrile hydratases and 1(OH) (CoIII versus CoII, respectively), 1(OH) was nonetheless an effective nitrile hydration catalyst, selectively producing acetamide over multiple turnovers.

Class Ib Ribonucleotide Reductases: Activation of a Peroxido-MnIIMnIII to Generate a Reactive Oxo-MnIIIMnIV Oxidant.

In the postulated catalytic cycle of class Ib Mn2 ribonucleotide reductases (RNRs), a MnII2 core is suggested to react with superoxide (O2·-) to generate peroxido-MnIIMnIII and oxo-MnIIIMnIV entities prior to proton-coupled electron transfer (PCET) oxidation of tyrosine. There is limited experimental support for this mechanism. We demonstrate that [MnII2(BPMP)(OAc)2](ClO4) (1, HBPMP = 2,6-bis[(bis(2 pyridylmethyl)amino)methyl]-4-methylphenol) was converted to peroxido-MnIIMnIII (2) in the presence of superoxide anion that converted to (µ-O)(µ-OH)MnIIIMnIV (3) via the addition of an H+-donor (p-TsOH) or (µ-O)2MnIIIMnIV (4) upon warming to room temperature. The physical properties of 3 and 4 were probed using UV-vis, EPR, X-ray absorption, and IR spectroscopies and mass spectrometry. Compounds 3 and 4 were capable of phenol oxidation to yield a phenoxyl radical via a concerted PCET oxidation, supporting the proposed mechanism of tyrosyl radical cofactor generation in RNRs. The synthetic models demonstrate that the postulated O2/Mn2/tyrosine activation mechanism in class Ib Mn2 RNRs is plausible and provides spectral insights into intermediates currently elusive in the native enzyme.

Synthesis, Characterisation, and Functionalisation of Charged Two-Dimensional MoS2.

The applications of exfoliated MoS2 are limited by its inert surface and poor interface. We have activated the surface of exfoliated 2H-MoS2 by reacting it with NaBH4 , forming an n-doped material as demonstrated by a negative zeta-potential value ζ=-25 mV and a 20 nm (0.05 eV) red-shift in its photoluminescence spectrum. The novel material's spectral properties were consistent with pristine 2H-MoS2 (as determined by HR-TEM, XPS, pXRD, DRIFT, TGA, and Raman spectroscopy). Importantly, it was readily dispersed in H2 O unlike 2H-MoS2 . Its dispersibility properties were explored for a variety of solvents and could be directly correlated with the relative permittivity of the respective solvents. The charged 2H-MoS2 reacted readily with an organo-iodide to deliver functionalized 2H-MoS2 . Our approach delivers aqueous dispersions of semiconducting 2H-MoS2 , without additives or chemical functionalities, and allows for controlled and facile functionalization of 2H-MoS2 opening multiple new avenues of semi-conducting MoS2 application.

Synthesis and Characterization of a Masked Terminal Nickel-Oxide Complex.

In exploring terminal nickel-oxo complexes, postulated to be the active oxidant in natural and non-natural oxidation reactions, we report the synthesis of the pseudo-trigonal bipyramidal NiII complexes (K)[NiII (LPh )(DMF)] (1[DMF]) and (NMe4 )2 [NiII (LPh )(OAc)] (1[OAc]) (LPh =2,2',2''-nitrilo-tris-(N-phenylacetamide); DMF=N,N-dimethylformamide; - OAc=acetate). Both complexes were characterized using NMR, FTIR, ESI-MS, and X-ray crystallography, showing the LPh ligand to bind in a tetradentate fashion, together with an ancillary donor. The reaction of 1[OAc] with peroxyphenyl acetic acid (PPAA) resulted in the formation of [(LPh )NiIII -O-H⋅⋅⋅OAc]2- , 2, that displays many of the characteristics of a terminal Ni=O species. 2 was characterized by UV-Vis, EPR, and XAS spectroscopies and ESI-MS. 2 decayed to yield a NiII -phenolate complex 3 (through aromatic electrophilic substitution) that was characterized by NMR, FTIR, ESI-MS, and X-ray crystallography. 2 was capable of hydroxylation of hydrocarbons and epoxidation of olefins, as well as oxygen atom transfer oxidation of phosphines at exceptional rates. While the oxo-wall remains standing, this complex represents an excellent example of a masked metal-oxide that displays all of the properties expected of the ever elusive terminal M=O beyond the oxo-wall.

Hydrocarbon Oxidation by a Porphyrin-π-Cation Radical Complex.

Heme and chlorin π-cation radical oxidants are widely implicated in biological and synthetic oxidation catalysis. Little insight into the role of π-cation radicals in proton coupled electron transfer (PCET) oxidation is available. We prepared a NiII -porphyrin-π-cation complex ([NiII (P⋅+ )]) and found it to be capable of the oxidation of a variety of simple hydrocarbon substrates. Interestingly, some of the products were hydroxylated, with ([NiII (P⋅+ )]) working in concert with atmospheric O2 to yield hydroxylated hydrocarbons. Kinetic data suggested that the porphyrin-π-cation radical species oxidised substrates through a concerted PCET mechanism, where the porphyrin-π-cation radical accepted the electron, and the proton was transferred to a free anion. Our findings highlight the potential role of π-cation radicals as hydrocarbon activators, demonstrating that porphyrin ligand non-innocence could be a readily manipulated resource for oxidation catalyst development.

Tuning the Photo-electrochemical Performance of RuII -Sensitized Two-Dimensional MoS2.

Covalently tethering photosensitizers to catalytically active 1T-MoS2 surfaces holds great promise for the solar-driven hydrogen evolution reaction (HER). Herein, we report the preparation of two new RuII -complex-functionalized MoS2 hybrids [RuII (bpy)2 (phen)]-MoS2 and [RuII (bpy)2 (py)Cl]-MoS2 . The influence of covalent functionalization of chemically exfoliated 1T-MoS2 with coordinating ligands and RuII complexes on the HER activity and photo-electrochemical performance of this dye-sensitized system was studied systematically. We find that the photo-electrochemical performance of this RuII -complex-sensitized MoS2 system is highly dependent on the surface extent of photosensitizers and the catalytic activity of functionalized MoS2 . The latter was strongly affected by the number and the kind of functional groups. Our results underline the tunability of the photovoltage generation in this dye-sensitized MoS2 system by manipulation of the surface functionalities, which provides a practical guidance for smart design of future dye-sensitized MoS2 hydrogen production devices towards improved the photofuel conversion efficiency.

Comparing Metal-Halide and -Oxygen Adducts in Oxidative C/O-H Activation: AuIII-Cl versus AuIII-OH.

High-valent metal-halides have come to prominence as highly effective oxidants. A direct comparison of their efficacy against that of traditional metal-oxygen adducts is needed. [AuIII(Cl)(terpy)](ClO4)2 (1; terpy = 2,2':6',2-terpyridine) readily oxidized substrates bearing O-H and C-H bonds via a hydrogen atom transfer mechanism. A direct comparison with [AuIII(OH)(terpy)](ClO4)2 (2) showed that 1 was a kinetically superior oxidant with respect to 2 for all substrates tested. We ascribe this to the greater thermodynamic driving force imbued by the Cl ligand versus the OH ligand.

Rapid Iron(III)-Fluoride-Mediated Hydrogen Atom Transfer.

We anticipate high-valent metal-fluoride species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude of the H-F bond (in the product) that drives HAT oxidation. We prepared a dimeric FeIII (F)-F-FeIII (F) complex (1) by reacting [FeII (NCCH3 )2 (TPA)](ClO4 )2 (TPA=tris(2-pyridylmethyl)amine) with difluoro(phenyl)-λ3 -iodane (difluoroiodobenzene). 1 was a sluggish oxidant, however, it was readily activated by reaction with Lewis or Brønsted acids to yield a monomeric [FeIII (TPA)(F)(X)]+ complex (2) where X=F/OTf. 1 and 2 were characterized using NMR, EPR, UV/Vis, and FT-IR spectroscopies and mass spectrometry. 2 was a remarkably reactive FeIII reagent for oxidative C-H activation, demonstrating reaction rates for hydrocarbon HAT comparable to the most reactive FeIII and FeIV oxidants.

Phenol Oxidation by a Nickel(III)-Fluoride Complex: Exploring the Influence of the Proton Accepting Ligand in PCET Oxidation.

In order to gain insight into the influence of the H+ -accepting terminal ligand in high-valent oxidant mediated proton coupled electron transfer (PCET) reactions, the reactivity of a high valent nickel-fluoride complex [NiIII (F)(L)] (2, L=N,N'-(2,6-dimethylphenyl)-2,6-pyridinecarboxamidate) with substituted phenols was explored. Analysis of kinetic data from these reactions (Evans-Polanyi, Hammett, and Marcus plots, and KIE measurements) and the formed products show that 2 reacted with electron rich phenols through a hydrogen atom transfer (HAT, or concerted PCET) mechanism and with electron poor phenols through a stepwise proton transfer/electron transfer (PT/ET) reaction mechanism. The analogous complexes [NiIII (Z)(L)] (Z=Cl, OCO2 H, O2 CCH3 , ONO2 ) reacted with all phenols through a HAT mechanism. We explore the reason for a change in mechanism with the highly basic fluoride ligand in 2. Complex 2 was also found to react one to two orders of magnitude faster than the corresponding analogous [NiIII (Z)(L)] complexes. This was ascribed to a high bond dissociation free energy value associated with H-F (135 kcal mol-1 ), which is postulated to be the product formed from PCET oxidation by 2 and is believed to be the driving force for the reaction. Our findings show that high-valent metal-fluoride complexes represent a class of highly reactive PCET oxidants.

Hydrogen Atom Transfer Oxidation by a Gold-Hydroxide Complex.

AuIII-oxygen adducts have been implicated as intermediates in homogeneous and heterogeneous Au oxidation catalysis, but their reactivity is under-explored. Complex 1, ([AuIII(OH)(terpy)](ClO4)2, (terpy = 2,2':6',2-terpyridine), readily oxidized substrates bearing C-H and O-H bonds. Kinetic analysis revealed that the oxidation occurred through a hydrogen atom transfer (HAT) mechanism. Stable radicals were detected and quantified as products of almost quantitative HAT oxidation of alcohols by 1. Our findings highlight the possible role of AuIII-oxygen adducts in oxidation catalysis and the capability of late transition metal-oxygen adducts to perform proton coupled electron transfer.

Oxo-Free Hydrocarbon Oxidation by an Iron(III)-Isoporphyrin Complex.

Metal-halides that perform proton coupled electron-transfer (PCET) oxidation are an important new class of high-valent oxidant. In investigating metal-dihalides, we reacted [FeIII(Cl)(T(OMe)PP)] (1, T(OMe)PP = meso-tetra(4-methoxyphenyl)porphyrinyl) with (dichloroiodo)benzene. An FeIII-meso-chloro-isoporphyrin complex [FeIII(Cl)2(T(OMe)PP-Cl)] (2) was obtained. 2 was characterized by electronic absorption, 1H NMR, EPR, and X-ray absorption spectroscopies and mass spectrometry with support from computational analyses. 2 was reacted with a series of hydrocarbon substrates. The measured kinetic data exhibited a nonlinear behavior, whereby the oxidation followed a hydrogen-atom-transfer (HAT) PCET mechanism. The meso-chlorine atom was identified as the HAT agent. In one case, a halogenated product was identified by mass spectrometry. Our findings demonstrate that oxo-free hydrocarbon oxidation with heme systems is possible and show the potential for iron-dihalides in oxidative hydrocarbon halogenation.

Fast Hydrocarbon Oxidation by a High-Valent Nickel-Fluoride Complex.

In the search for highly reactive oxidants we have identified high-valent metal-fluorides as a potential potent oxidant. The high-valent Ni-F complex [NiIII (F)(L)] (2, L=N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate) was prepared from [NiII (F)(L)]- (1) by oxidation with selectfluor. Complexes 1 and 2 were characterized by using 1 H/19 F NMR, UV-vis, and EPR spectroscopies, mass spectrometry, and X-ray crystallography. Complex 2 was found to be a highly reactive oxidant in the oxidation of hydrocarbons. Kinetic data and products analysis demonstrate a hydrogen atom transfer mechanism of oxidation. The rate constant determined for the oxidation of 9,10-dihydroanthracene (k2 =29 m-1 s-1 ) compared favorably with the most reactive high-valent metallo-oxidants. Complex 2 displayed reaction rates 2000-4500-fold enhanced with respect to [NiIII (Cl)(L)] and also displayed high kinetic isotope effect values. Oxidative hydrocarbon and phosphine fluorination was achieved. Our results provide an interesting direction in designing catalysts for hydrocarbon oxidation and fluorination.

Preparation and Characterisation of a Bis-µ-Hydroxo-NiIII 2 Complex.

Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-µ-hydroxo-NiII 2 complex (1) supported by a new dicarboxamidate ligand (N,N'-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e- oxidant (NH4 )2 [CeIV (NO3 )6 ] with 1 at -45 °C showed the formation of the high-valent species 2 and 3, containing NiII NiIII and NiIII 2 diamond cores, respectively, maintaining the bis-µ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-µ-hydroxide-NiIII 2 3 was capable of oxidizing substrates at -45 °C at rates greater than that of the most reactive bis-µ-oxo-NiIII complexes reported to date.

Carboxamidate Ligand Noninnocence in Proton Coupled Electron Transfer.

Recent breakthroughs have brought into question the innocence (or not) of carboxamidate donor ligands in the reactivity of high-valent oxidants. To test the reactivity properties of high-valent carboxamidate complexes, [NiII(tBu-terpy)(L)] (1, tBu-terpy = 4,4',4''-tri- tert-butyl-2,2';6',2″-terpyridine; L = N, N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate) was prepared and converted to [NiIII(tBu-terpy)(L)]+ (2) using ceric ammonium nitrate. 2 was characterized using electronic absorption and electron paramagnetic resonance spectroscopies and electrospray ionization mass spectrometry. 2 was found to be a capable oxidant of phenols and through kinetic analysis was found to oxidize these substrates via a nonconcerted or partially concerted proton coupled electron transfer (PCET) mechanism. The products of PCET oxidation of phenols by 2 were phenoxyl radical and the protonated form of 1, 1H+. 1H+ was crystallographically characterized providing convincing evidence of 1's ability to act as a proton acceptor. We demonstrate that the complex remained intact through a full cycle of oxidation of 1 to 2, PCET of 2 to yield 1H+, and deprotonation of 1H+ to yield 1 followed by reoxidation of 1 to yield 2. The N-H bond dissociation energy of the protonated amide in 1H+ was determined to be 84 kcal/mol. Our findings illuminate the role carboxamidate ligands can play in PCET oxidation.

High-Valent d7 NiIII versus d8 CuIII Oxidants in PCET.

Oxygenases have been postulated to utilize d4 FeIV and d8 CuIII oxidants in proton-coupled electron transfer (PCET) hydrocarbon oxidation. In order to explore the influence the metal ion and d-electron count can hold over the PCET reactivity, two metastable high-valent metal-oxygen adducts, [NiIII(OAc)(L)] (1b) and [CuIII(OAc)(L)] (2b), L = N,N'-(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamidate, were prepared from their low-valent precursors [NiII(OAc)(L)]- (1a) and [CuII(OAc)(L)]- (2a). The complexes 1a/b-2a/b were characterized using nuclear magnetic resonance, Fourier transform infrared, electron paramagnetic resonance, X-ray diffraction, and absorption spectroscopies and mass spectrometry. Both complexes were capable of activating substrates through a concerted PCET mechanism (hydrogen atom transfer, HAT, or concerted proton and electron transfer, CPET). The reactivity of 1b and 2b toward a series of para-substituted 2,6-di-tert-butylphenols (p-X-2,6-DTBP; X = OCH3, C(CH3)3, CH3, H, Br, CN, NO2) was studied, showing similar rates of reaction for both complexes. In the oxidation of xanthene, the d8 CuIII oxidant displayed a small increase in the rate constant compared to that of the d7 NiIII oxidant. The d8 CuIII oxidant was capable of oxidizing a large family of hydrocarbon substrates with bond dissociation enthalpy (BDEC-H) values up to 90 kcal/mol. It was previously observed that exchanging the ancillary anionic donor ligand in such complexes resulted in a 20-fold enhancement in the rate constant, an observation that is further enforced by comparison of 1b and 2b to the literature precedents. In contrast, we observed only minor differences in the rate constants upon comparing 1b to 2b. It was thus concluded that in this case the metal ion has a minor impact, while the ancillary donor ligand yields more kinetic control over HAT/CPET oxidation.

A MnII MnIII -Peroxide Complex Capable of Aldehyde Deformylation.

Ribonucleotide reductases (RNRs) are essential enzymes required for DNA synthesis. In class Ib Mn2 RNRs superoxide (O2.- ) was postulated to react with the MnII2 core to yield a MnII MnIII -peroxide moiety. The reactivity of complex 1 ([MnII2 (O2 CCH3 )2 (BPMP)](ClO4 ), where HBPMP=2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol) towards O2.- was investigated at -90 °C, generating a metastable species, 2. The electronic absorption spectrum of 2 displayed features (λmax =440, 590 nm) characteristic of a MnII MnIII -peroxide species, representing just the second example of such. Electron paramagnetic resonance and X-ray absorption spectroscopies, and mass spectrometry supported the formulation of 2 as a MnII MnIII -peroxide complex. Unlike all other previously reported Mn2 -peroxides, which were unreactive, 2 proved to be a capable oxidant in aldehyde deformylation. Our studies provide insight into the mechanism of O2 -activation in Class Ib Mn2 RNRs, and the highly reactive intermediates in their catalytic cycle.

Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex.

Oxo-metal-halide moieties have often been implicated as C-H bond activating oxidants with the terminal oxo-metal entity identified as the electrophilic oxidant. The electrophilic reactivity of metal-halide species has not been investigated. We have prepared a high-valent nickel-halide complex [NiIII(Cl)(L)] (2, L = N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide) by one-electron oxidation of a [NiII(Cl)(L)]- precursor. 2 was characterized using electronic absorption, electron paramagnetic resonance, and X-ray absorption spectroscopies and mass spectrometry. 2 reacted readily with substrates containing either phenolic O-H or hydrocarbon C-H bonds. Analysis of the Hammett, Evans-Polanyi, and Marcus relationships between the determined rate constants and substrate pKa, X-H bond dissociation energy, and oxidation potential, respectively, was performed. Through this analysis, we found that 2 reacted by a hydrogen atom transfer (HAT) mechanism. Our findings shine light on enzymatic high-valent oxo-metal-halide oxidants and open new avenues for oxidative halogenation catalyst design.

Modulation of Nickel Pyridinedicarboxamidate Complexes to Explore the Properties of High-valent Oxidants.

High-valent Ni oxidants have been implicated in hydrocarbon oxidation catalysis, however, little is understood about the properties of these oxidants. Herein, a family of NiII complexes supported by a pyridinedicarboxamidate ligand and different ancillary ligands was synthesized. The series spans coordination numbers 4, 5, and 6, and contains neutral, mono- and di-anionic donor types. X-ray crystallography and magnetic measurements showed that the 4-coordinate complexes were square planar and low spin (S=0) and the 5- and 6-coordinate were intermediate spin (S=1). The NiII complexes could be oxidized by one electron to form a series of metastable NiIII species. EPR analysis confirmed their description as S=1/2 NiIII compounds with signal shape and hyperfine coupling dependent on the coordination environment. The oxidation of phenols by the NiIII species was probed, providing evidence for a correlation between oxidizing power and electron-donating properties of the supporting ligands. Critically, we found that the pyridinedicarboxamidate ligand may be a non-innocent proton acceptor in the oxidation reactions.

RuII Photosensitizer-Functionalized Two-Dimensional MoS2 for Light-Driven Hydrogen Evolution.

Metallic-phase molybdenum disulfide (1T-MoS2 ) nanosheets have proven to be highly active in the hydrogen evolution reaction (HER). We describe construction of photosensitizer functionalized 1T-MoS2 by covalently tethering the molecular photosensitizer [RuII (bpy)3 ]2+ (bpy=2,2'-bipyridine) on 1T-MoS2 nanosheets. This was achieved by covalently tethering the bpy ligand to 1T-MoS2 nanosheets, and subsequent complexation with [RuII (bpy)2 Cl2 ] to yield [RuII (bpy)3 ]-MoS2 . The obtained [RuII (bpy)3 ]-MoS2 nanosheets were characterized using infra-red, electronic absorption, X-ray photoelectron, and Raman spectroscopies, X-ray powder diffraction and electron microscopy. The fabricated material exhibited a significant improvement of photocurrent and HER performance, demonstrating the potential of such two-dimensional [RuII (bpy)3 ]-MoS2 constructs in photosensitized HER.

Mimicking Class†I b Mn2 -Ribonucleotide Reductase: A MnII2 Complex and Its Reaction with Superoxide.

A fascinating discovery in the chemistry of ribonucleotide reductases (RNRs) has been the identification of a dimanganese (Mn2 ) active site in class I b RNRs that requires superoxide anion (O2.- ), rather than dioxygen (O2 ), to access a high-valent Mn2 oxidant. Complex 1 ([Mn2 (O2 CCH3 )(N-Et-HPTB)](ClO4 )2 , N-Et-HPTB=N,N,N',N'-tetrakis(2-(1-ethylbenzimidazolyl))-2-hydroxy-1,3-diaminopropane) was synthesised in high yield (90 %). 1 was reacted with O2.- at -40 °C resulting in the formation of a metastable species (2). 2 displayed electronic absorption features (λmax =460, 610 nm) typical of a Mn-peroxide species and a 29-line EPR signal typical of a MnII MnIII entity. Mn K-edge X-ray absorption near-edge spectroscopy (XANES) suggested a formal oxidation state change of MnII2 in 1 to MnII MnIII for 2. Electrospray ionisation mass spectrometry (ESI-MS) suggested 2 to be a MnII MnIII -peroxide complex. 2 was capable of oxidizing ferrocene and weak O-H bonds upon activation with proton donors. Our findings provide support for the postulated mechanism of O2.- activation at class I b Mn2 RNRs.