Utilizing EPR spectroscopy to investigate the liquid adsorption properties of bimetallic MIL-53(Al/Cr) MOF.

The flexibility of the MIL-53(M) metal-organic framework (MOF) has been elucidated through various characterization methodologies, particularly in gas and liquid adsorption processes. However, to the best of our knowledge, there has been no prior electron paramagnetic resonance (EPR) characterization of liquid-phase adsorption in the MOF MIL-53(M), which offers insights into local geometric changes at the oxygen octahedron containing the metal ions of the framework. In this study, we investigate, for the first time, the pore transformations within the MIL-53(Al0.99Cr0.01) framework during liquid-phase adsorption using EPR spectroscopy. Our investigation concentrates explicitly on the adsorption of pure solvents, including water, methanol, ethanol, isopropanol, pyridine, and mixed water/methanol phases. The EPR spectroscopy on the (Al0.99Cr0.01) MOF has allowed us to witness and comprehend the transitions between the narrow pore and large pore phases by examining changes in the zero-field splitting parameters of the S = 3/2 Cr(iii) species. Of all the solvents examined, a robust and distinct spectral feature observed during methanol adsorption unequivocally indicates the pore opening.

A Continuous-Wave EPR Investigation into the Photochemical Transformations of the Chromium(I) Carbonyl Complex [Cr(CO)4bis(diphenylphosphino)]+ and Reactivity with 1-hexene.

Chromium complexes containing a bis(diphenylphosphino) ligand have attracted significant interest over many years due to their potential as active catalysts for ethylene oligomerisation when combined with suitable co-catalysts such as triethylaluminium (TEA) or methylaluminoxane (MAO). While there has been considerable attention devoted to the possible reaction intermediates and the nature of the Cr oxidation states involved, the potential UV photoactivity of the Cr(I) complexes has so far been overlooked. Therefore, to explore the photoinduced transformations of bis(diphenylphosphino) stabilized Cr(I) complexes, we used continuous-wave (CW) EPR to study the effects of UV radiation on a cationic [Cr(CO)4(dppp)]+[Al(OC(CF3)3)4]- complex (1), where dppp represents the 1,3 bis-(diphenylphosphino)propane ligand, Ph2P(C3H6)PPh2. Our preliminary investigations into the photochemistry of this complex revealed that [Cr(CO)4(dppp)]+ (1) can be readily photo-converted into an intermediate mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ complex (2) and eventually into a trans-[Cr(CO)2(dppp)2]+ complex (3) in solution at room temperature under UV-A light. Here, we show that the intermediate species (2) involved in this transformation can be identified by EPR at much lower temperature (140 K) and at a specific wavelength (highlighting the wavelength dependency of the reaction). In addition, small amounts of a 'piano-stool'-type complex, namely [Cr(CO)2(dppp-η6-arene)]+ (4), can also be formed during the photoconversion of [Cr(CO)4(dppp)]+ using UV-A light. There was no evidence for the formation of the [Cr(L-bis-η6-arene)]+ complex (5) in these UV irradiation experiments. For the first time, we also evidence the formation of a 1-hexene coordinated [Cr(CO)3(dppp)(1-hexene)]+ complex (6) following UV irradiation of [Cr(CO)4(dppp)]+ in the presence of 1-hexene; this result demonstrates the unprecedented opportunity for exploiting light activation during Cr-driven olefin oligomerisation catalysis, instead of expensive, difficult-to-handle, and hazardous chemical activators.

Unveiling the atomistic and electronic structure of NiII-NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling.

The nature of the chemical bonding between NO and open-shell NiII ions docked in a metal-organic framework is fully characterized by EPR spectroscopy and computational methods. High-frequency EPR experiments reveal the presence of unsaturated NiII ions displaying five-fold coordination. Upon NO adsorption, in conjunction with advanced EPR methodologies and DFT/CASSCF modelling, the covalency of the metal-NO and metal-framework bonds is directly quantified. This enables unravelling the complex electronic structure of NiII-NO species and retrieving their microscopic structure.

Extreme g-Tensor Anisotropy and Its Insensitivity to Structural Distortions in a Family of Linear Two-Coordinate Ni(I) Bis-N-heterocyclic Carbene Complexes.

We report a new series of homoleptic Ni(I) bis-N-heterocyclic carbene complexes with a range of torsion angles between the two ligands from 68° to 90°. Electron paramagnetic resonance measurements revealed a strongly anisotropic g-tensor in all complexes with a small variation in g∥ ∼ 5.7-5.9 and g⊥ ∼ 0.6. The energy of the first excited state identified by variable-field far-infrared magnetic spectroscopy and SOC-CASSCF/NEVPT2 calculations is in the range 270-650 cm-1. Magnetic relaxation measured by alternating current susceptibility up to 10 K is dominated by Raman and direct processes. Ab initio ligand-field analysis reveals that a torsion angle of <90° causes the splitting between doubly occupied dxz and dyz orbitals, which has little effect on the magnetic properties, while the temperature dependence of the magnetic relaxation appears to have no correlation with the torsion angle.

A novel dual mode X-band EPR resonator for rapid in situ microwave heating.

A unique dual mode X-band Continuous Wave (CW) EPR resonator designed for simultaneous EPR measurement and rapid microwave (MW) induced sample heating is described. Chemical reactions subjected to a flow of energy and matter can be perturbed away from the thermodynamic equilibrium by imposing a rapid shock or physical change to the system. Depending on the magnitude of the perturbation, these changes can dictate the subsequent evolution of the entire system, allowing for instance to populate non-equilibrium reactive intermediate states. Temperature jump (T-jump) experiments are a common method to achieve such perturbations. Most T-jump experiments are based on Joule Heating methods or IR lasers. Here we demonstrate the principle of rapid sample heating based on microwaves. The benefits of MW heating include (i) rapid and efficient heating (i.e. using a tuned resonant cavity, >99% efficient power transfer to the sample can be achieved), and (ii) volumetric heating (i.e. the entire sample volume rises in temperature at once, since heat is generated in the sample instead of being transferred to it). Accordingly, the key concept of the design is the use of a cavity resonator allowing EPR detection (at 9.5 GHz) and simultaneous sample heating (at 6.1 GHz). Temperature increments of 50 °C within a few seconds are possible. This is evidenced and illustrated here by probing the temperature-induced variation of the rotational dynamics of 16-doxyl stearic acid methyl ester (16-DSE) spin probe grafted on the surface of sodium dodecyl sulphate (SDS) micelles in water, as well as copper (II) acetylacetonate in chloroform. Rapid changes in the rotational dynamics of the paramagnetic centres provide direct evidence for the in situ and simultaneous EPR measurement-heating capabilities of the resonator. Improvements afforded by the use of pulsed MW sources will enable faster heating time scales to be achieved. In the longer term, this current study demonstrates the simple and direct possibilities for using MW heating as a means of performing T-jump experiments.

Twisting the arm: structural constraints in bicyclic expanded-ring N-heterocyclic carbenes.

A series of diaryl, mono-aryl/alkyl and dialkyl mono- and bicyclic expanded-ring N-heterocyclic carbenes (ER-NHCs) have been prepared and their complexation to Au(i) investigated through the structural analysis of fifteen Au(NHC)X and/or [Au(NHC)2]X complexes. The substituted diaryl 7-NHCs are the most sterically encumbered with large buried volume (%VB) values of 40-50% with the less flexible six-membered analogues having %VB values at least 5% smaller. Although the bicyclic systems containing fused 6- and 7-membered rings (6,7-NHCs) are constrained with relatively acute NCN bond angles, they have the largest %VB values of the dialkyl derivatives reported here, a feature related to the fixed conformation of the heterocyclic rings and the compressional effect of a pre-set methyl substituent.

Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR Spectroscopy.

UV-induced photochemical transformations of the paramagnetic [Cr(CO)4(Ph2PCH2CH2CH2PPh2)]+ complex (abbreviated [Cr(CO)4(dppp)]+) in dichloromethane was investigated by CW EPR spectroscopy. Room-temperature UV irradiation results in the rapid transformation of [Cr(CO)4(dppp)]+ into trans-[Cr(CO)2(dppp)2]+. However, low-temperature (77-120 K) UV irradiation reveals the presence of an intermediate mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ complex which photochemically transforms into trans-[Cr(CO)2(dppp)2]+. The derived spin Hamiltonian parameters for these complexes were confirmed by DFT calculations. The photoinduced reaction is shown to be concentration-dependent, leading to a distribution of the three complexes ([Cr(CO)4(dppp)]+, mer-[Cr(CO)3(κ1-dppp)(κ 2-dppp)]+, and trans-[Cr(CO)2(dppp)2]+). A bimolecular photoinduced mechanism is proposed to account for the formation of mer-[Cr(CO)3(κ1-dppp)(κ2-dppp)]+ and trans-[Cr(CO)2(dppp)2]+.

An EPR Investigation of Binding Environments by N-Donor Chelating Exchange Resins for Cu Extraction from Aqueous Media.

Chelating exchange resins (CERs) are now widely used for metal extraction in aqueous acidic media. Many of these CERs contain surface N-donor ligands, such as di(2-picolylamine) (BPA) and picolylamine (PA), which are highly selective for Cu(II) uptake. Two such widely used resins are Dowex M4195 and CuWRAM. Surprisingly, very little is known about the Cu(II) binding environments on the exchange resins, particularly at variable concentrations and pH's, and therefore we used EPR spectroscopy to investigate this binding. The broad EPR spectra of the Cu(II) loaded resins are quite complex, indicating the presence of multiple Cu(II) binding environments. By preparing a series of well-defined [CuII(PA) x] and [CuII(BPA) x] complexes and studying their EPR and UV-vis spectra, the individual Cu(II) species contributing to the broad and overlapping EPR spectra of the loaded resins were identified. For Dowex M4195, [CuII(BPA)](H2O) m and [CuII(BPA)2] complexes are most dominant, whereas for CuWRAM two dominant species including [CuII(PA)2](H2O) m and [CuII(PA)3] were identified. Notably, [CuII(PA)](H2O) m was not present in this sample. The experimental spin Hamiltonian parameters for all these species were in good agreement with the density functional theory derived values. Additional intermolecular Cu(II) species were identified on both resins, labeled [CuII(BPA) x(BPA) y(H2O) n] and [CuII(PA) x(PA) y(H2O) n]. The presence of coordinated water in these intermolecular anchored sites was confirmed in a series of dehydration-rehydration experiments. Furthermore, a series of acid elution experiments also confirmed that these species are less strongly coordinated to the resins compared to the intramolecular species [CuII(BPA)](H2O) m, [CuII(BPA)2], [CuII(PA)2](H2O) m, and [CuII(PA)3]. Finally, while equilibrium batch uptake measurements revealed that the CuWRAM material had a much lower Cu(II) capacity compared to the polymeric Dowex material, the adsorbed copper can be recovered more efficiently using acid elution.

Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br].

Bromide abstraction from the three-coordinate Ni(i) ring-expanded N-heterocyclic carbene complex [Ni(6-Mes)(PPh3)Br] (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) with TlPF6 in THF yields the T-shaped cationic solvent complex, [Ni(6-Mes)(PPh3)(THF)][PF6] (2), whereas treatment with NaBArF4 in Et2O affords the dimeric Ni(i) product, [{Ni(6-Mes)(PPh3)}2(µ-Br)][BArF4] (3). Both 2 and 3 act as latent sources of the cation [Ni(6-Mes)(PPh3)]+, which can be trapped by CO to give [Ni(6-Mes)(PPh3)(CO)]+ (5). Addition of [(Et3Si)2(µ-H)][B(C6F5)4] to 1 followed by work up in toluene results in the elimination of phosphine as well as halide to afford a co-crystallised mixture of [Ni(6-Mes)(η2-C6H5Me)][B(C6F5)4] (4), and [6MesHC6H5Me][B(C6F5)4]. Treatment of 1 with sodium salts of more strongly coordinating anions leads to substitution products. Thus, NaBH4 yields the neutral, diamagnetic dimer [{Ni(6-Mes)}2(BH4)2] (6), whereas NaBH3(CN) gives the paramagnetic monomeric cyanotrihydroborate complex [Ni(6-Mes)(PPh3)(NCBH3)] (7). Treatment of 1 with NaOtBu/NHPh2 affords the three-coordinate Ni(i) amido species, [Ni(6-Mes)(PPh3)(NPh2)] (8). The electronic structures of 2, 5, 7 and 8 have been analysed in comparison to that of previously reported 1 using a combination of EPR spectroscopy and density functional theory.

Customizing Photoredox Properties of PXX-based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals.

Here we describe the synthesis of electron-rich PXX derivatives in which the energy levels of the excited states have been rigidly shifted through the insertion of imide groups. This has allowed the development of a new series of oxygen-doped photoredox-active chromophores with improved oxidizing and reducing properties. Capitalizing on the dehalogenation of organic halides as a model reaction, we could investigate the photooxidative and photoreductive potential of these molecules in model chemical transformations. Depending on the substrate, solvent and dye the reaction mechanism can follow different paths. This prompted us to consider the first chemoselective transformation protocol, in which two different C-Br bonds could be chemoselectively reacted through the sequential photoactivation of two different colorants.

Understanding the Coordination Modes of [Cu(acac)2(imidazole)n=1,2] Adducts by EPR, ENDOR, HYSCORE, and DFT Analysis.

The interaction of imidazole with a [Cu(acac)2] complex was studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), hyperfine sublevel correlation spectroscopy (HYSCORE), and density functional theory (DFT). At low Im ratios (Cu:Im 1:10), a 5-coordinate [Cu(acac)2Imn=1] monoadduct is formed in frozen solution with the spin Hamiltonian parameters g1 = 2.063, g2 = 2.063, g3 = 2.307, A1 = 26, A2 = 15, and A3 = 472 MHz with Im coordinating along the axial direction. At higher Im concentrations (Cu:Im 1:50), a 6-coordinate [Cu(acac)2Imn=2] bis-adduct is formed with the spin Hamiltonian parameters g1 = 2.059, g2 = 2.059, g3 = 2.288, A1 = 30, A2 = 30, and A3 = 498 MHz with a poorly resolved 14N superhyperfine pattern. The isotropic EPR spectra revealed a distribution of species ([Cu(acac)2], [Cu(acac)2Imn=1], and [Cu(acac)2Imn=2]) at Cu:Im ratios of 1:0, 1:10, and 1:50. The superhyperfine pattern originates from two strongly coordinating N3 imino nitrogens of the Im ring. Angular selective 14N ENDOR analysis revealed the NA tensor of [34.8, 43.5, 34.0] MHz, with e2qQ/h = 2.2 MHz and η = 0.2 for N3. The hyperfine and quadrupole values for the remote N1 amine nitrogens (from HYSCORE) were found to be [1.5, 1.4, 2.5] MHz with e2qQ/h = 1.4 MHz and η = 0.9. 1H ENDOR also revealed three sets of HA tensors corresponding to the nearly equivalent H2/H4 protons in addition to the H5 and H1 protons of the Im ring. The spin Hamiltonian parameters for the geometry optimized structures of [Cu(acac)2Imn=2], including cis-mixed plane, trans-axial, and trans-equatorial, were calculated. The best agreement between theory and experiment indicated the preferred coordination is trans-equatorial [Cu(acac)2Imn=2]. A number of other Im derivatives were also investigated. 4(5)-methyl-imidazole forms a [Cu(acac)2(Im-3)n=2] trans-equatorial adduct, whereas the bulkier 2-methyl-imidazole (Im-2) and benzimidazole (Im-4) form the [Cu(acac)2(Im-2,4)n=1] monoadduct only. Our data therefore show that subtle changes in the substrate structure lead to controllable changes in coordination behavior, which could in turn lead to rational design of complexes for use in catalysis, imaging, and medicine.

Catalytic Partial Oxidation of Cyclohexane by Bimetallic Ag/Pd Nanoparticles on Magnesium Oxide.

The liquid-phase oxidation of cyclohexane to cyclohexanol and cyclohexanone was investigated by synthesizing and testing an array of heterogeneous catalysts comprising: monometallic Ag/MgO, monometallic Pd/MgO and a set of bimetallic AgPd/MgO catalysts. Interestingly, Ag/MgO was capable of a conversion comparable to current industrial routes of approximately 5 %, and with a high selectivity (up to 60 %) to cyclohexanol, thus making Ag/MgO an attractive system for the synthesis of intermediates for the manufacture of nylon fibres. Furthermore, following the doping of Ag nanoparticles with Pd, the conversion increased up to 10 % whilst simultaneously preserving a high selectivity to the alcohol. Scanning transmission electron microscopy and energy dispersive spectroscopy of the catalysts showed a systematic particle-size-composition variation with the smaller Ag-Pd nanoparticles being statistically richer in Pd. Analysis of the reaction mixture by electron paramagnetic resonance (EPR) spectroscopy coupled with the spin-trapping technique showed the presence of large amounts of alkoxy radicals, thus providing insights for a possible reaction mechanism.

Influence of Ring-Expanded N-Heterocyclic Carbenes on the Structures of Half-Sandwich Ni(I) Complexes: An X-ray, Electron Paramagnetic Resonance (EPR), and Electron Nuclear Double Resonance (ENDOR) Study.

Potassium graphite reduction of the half-sandwich Ni(II) ring-expanded diamino/diamidocarbene complexes CpNi(RE-NHC)Br gave the Ni(I) derivatives CpNi(RE-NHC) (where RE-NHC = 6-Mes (1), 7-Mes (2), 6-MesDAC (3)) in yields of 40%-50%. The electronic structures of paramagnetic 1-3 were investigated by CW X-/Q-band electron paramagnetic resonance (EPR) and Q-band 1H electron nuclear double resonance (ENDOR) spectroscopy. While small variations in the g-values were observed between the diaminocarbene complexes 1 and 2, pronounced changes in the g-values were detected between the almost isostructural species (1) and diamidocarbene species (3). These results highlight the sensitivity of the EPR g-tensor to changes in the electronic structure of the Ni(I) centers generated by incorporation of heteroatom substituents onto the backbone ring positions. Variable-temperature EPR analysis also revealed the presence of a second Ni(I) site in 3. The experimental g-values for these two Ni(I) sites detected by EPR in frozen solutions of 3 are consistent with resolution on the EPR time scale of the disordered components evident in the X-ray crystallographically determined structure and the corresponding density functional theory (DFT)-calculated g-tensor. Q-band 1H ENDOR measurements revealed a small amount of unpaired electron spin density on the Cp rings, consistent with the calculated SOMO of complexes 1-3. The magnitude of the 1H A values for 3 were also notably larger, compared to 1 and 2, again highlighting the influence of the diamidocarbene on the electronic properties of 3.

EPR/ENDOR and Computational Study of Outer Sphere Interactions in Copper Complexes of Phenolic Oximes.

Copper complexes of the phenolic oxime family of ligands (3-X-salicylaldoximes) are used extensively as metal solvent extractants. Incorporation of electronegative substituents in the 3-position, ortho to the phenol group, can be used to buttress the interligand H-bonding, leading to an enhancement in extractant strength. However, investigation of the relevant H-bonding in these complexes can be exceedingly difficult. Here, we have combined EPR, ENDOR, DFT, and X-ray crystallography to study this effect. Analysis of the (1)H ENDOR data revealed a variation in the Cu···H(16) (oxime proton) distance from 2.92 Å for the unsubstituted complex [Cu(L(2))2] to 3.65 Å for the X = CH2N(C6H13)2 substituted complex [Cu(L(3))2]. DFT calculations showed that this variation is caused by changes to the length and strength of the H-bond between the oximic hydrogen and the phenolate oxygen. Noticeable changes to the Cu···H(15) (azomethine proton) distances and the Cu···N bonding parameters were also observed in the two complexes, as revealed through the (N)A and (N)Q ENDOR data. Distortions in the structure of the complex and variations in the oximic proton to phenolate oxygen H-bond strength caused by the substituent (X) were confirmed by DFT and X-ray crystallography. DFT directly evidenced the importance of the interaction between H(16) and the amine nitrogen of CH2N(C6H13)2 in the buttressed complex and indicated that the high strength of this interaction may not necessarily lead to an enhancement of copper extraction, as it can impose an unfavorable geometry in the inner coordination sphere of the complex. Therefore, ENDOR, DFT, and X-ray structural data all indicate that the aminomethyl substituent (X) ortho to the phenolic oxygen atom provides a particularly strong buttressing of interligand H-bonding in these copper complexes and that these outer sphere interactions can significantly influence structure and stability.

Structure determination of bound nitrogen-based adducts with copper(II) acetylacetonato; an EPR, ENDOR and DFT study.

The adducts of bis(acetylacetonato)­copper(II), [Cu(acac)2], formed with a range of nitrogen heterocycles including pyridine (2), methylpyridines (3,4,5), amino-methylpyridines (6,7) and diazines (8,9,10) were investigated in frozen solution using X-band EPR and 1H ENDOR spectroscopy. The small perturbations to the EPR spin Hamiltonian parameters (g and CuA) were consistent with the axial coordination of the nitrogen bases to Cu(II), and found to be dependent on both the basicity and steric influence of the coordinating substrate. The detailed structure of two adducts was then investigated by angular selective (1)H ENDOR and DFT. For the [Cu(acac)2](pyridine) adduct, axial coordination of the substrate was found to occur via the pyridine nitrogen as expected, producing a characteristic (1)H hyperfine coupling ((H)Ai = −2.6, −2.04, 4.7 MHz; ß = 36°; aiso = 0.2 MHz) arising from the ortho-(1)H in the ring 2 or 6 position. These results were confirmed by DFT. However, in the [Cu(acac)2](2-amino-6-methyl-pyridine) adduct, the ENDOR data revealed a substantially different (1)H hyperfine coupling ((H)Ai = −4.52, −3.35, 6.47 MHz; ß = 14°; aiso = −0.47 MHz) arising from the ­NH2 amino protons. Analysis of this experimentally derived tensor in conjunction with the calculated DFT tensors, revealed that the 2-amino-6-methyl-pyridine substrate binds to Cu(II) via the exocyclic amino pyridine nitrogen, but with a tilt angle of 20° of the pyridine ring away from the geometry optimised structure. These results reveal how important structural information on the coordination geometry of Cu(II) adducts can be obtained by (1)H ENDOR, but only when the complete angular dependency profile of the ENDOR data is thoroughly considered.

Expedient iron-catalyzed coupling of alkyl, benzyl and allyl halides with arylboronic esters.

While attractive, the iron-catalyzed coupling of arylboron reagents with alkyl halides typically requires expensive or synthetically challenging diphosphine ligands. Herein, we show that primary and secondary alkyl bromides and chlorides, as well as benzyl and allyl halides, can be coupled with arylboronic esters, activated with alkyllithium reagents, by using very simple iron-based catalysts. The catalysts used were either adducts of inexpensive and widely available diphosphines or, in a large number of cases, simply [Fe(acac)3] with no added co-ligands. In the former case, preliminary mechanistic studies highlight the likely involvement of iron(I)-phosphine intermediates.

A two-coordinate manganese(0) complex with an unsupported Mn-Mg bond: allowing access to low coordinate homo- and heterobimetallic compounds.

This study details the synthesis and characterization of an unprecedented two-coordinate, high-spin manganese(0) complex that incorporates an unsupported Mn-Mg bond, viz. L(†)MnMg((Mes)Nacnac) (L(†) = -N(Ar(†))(SiPr(i)3), Ar(†) = C6H2{C(H)Ph2}2Pr(i)-2,6,4; (Mes)Nacnac = [(MesNCMe)2CH](-); Mes = mesityl). This compound has been utilized as an "inorganic Grignard reagent" in the preparation of the first two-coordinate manganese(I) dimer, L(†)MnMnL* (L* = -N(Ar*)(SiMe3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4), and the related mixed valence, bis(amido)-hetereobimetallic complex, Mn(II)(µ-L(†))(µ-L*)Cr(0). It is also shown to act as a two-electron reducing agent in reactions with unsaturated substrates.

TMEDA in iron-catalyzed Kumada coupling: amine adduct versus homoleptic "ate" complex formation.

The reactions of iron chlorides with mesityl Grignard reagents and tetramethylethylenediamine (TMEDA) under catalytically relevant conditions tend to yield the homoleptic "ate" complex [Fe(mes)3 ](-) (mes=mesityl) rather than adducts of the diamine, and it is this ate complex that accounts for the catalytic activity. Both [Fe(mes)3 ](-) and the related complex [Fe(Bn)3 ](-) (Bn=benzyl) react faster with representative electrophiles than the equivalent neutral [FeR2 (TMEDA)] complexes. Fe(I) species are observed under catalytically relevant conditions with both benzyl and smaller aryl Grignard reagents. The X-ray structures of [Fe(Bn)3 ](-) and [Fe(Bn)4 ](-) were determined; [Fe(Bn)4 ](-) is the first homoleptic σ-hydrocarbyl Fe(III) complex that has been structurally characterized.

The benzaldehyde oxidation paradox explained by the interception of peroxy radical by benzyl alcohol.

Benzaldehyde readily undergoes autoxidation to form benzoic acid on exposure to air at room temperature. Yet it can be formed in high yield from, for example, benzyl alcohol by oxidation using a variety of procedures and catalysts. Here we report the evidence to resolve this apparent paradox. It is confirmed that benzyl alcohol (and a number of other alcohols), even at low concentrations in benzaldehyde, inhibits the autoxidation. Furthermore we report on the structural features required for inhibition. Electron paramagnetic resonance spin trapping experiments demonstrate that benzyl alcohol intercepts, by hydrogen atom transfer, the benzoylperoxy radicals that play a key role in benzaldehyde autoxidation. A similar inhibition effect has also been observed for the aliphatic octanal/1-octanol system.

Structure, EPR/ENDOR and DFT characterisation of a [Cu(II)(en)2](OTf)2 complex.

The Jahn-Teller distorted Cu(II) complex [Cu(en)2](OTf)2 1 (en = 1,2-diaminoethane) has been reported and characterised using X-ray crystallography, EPR and ENDOR spectroscopy, and DFT calculations. The solid state structure shows an intra- and inter-molecular hydrogen-bonded network via the N-H groups and the coordinated triflate anions. CW and pulsed EPR/ENDOR were used to determine the spin Hamiltonian parameters of the Cu(II) complex, which were in excellent agreement with the DFT. The structure of the complex, as determined by angular selective ENDOR, is also in good agreement with the crystal structure, confirming the axial coordination of the counter-ion(s) in the frozen solution. The small (14)N superhyperfine couplings are also consistent with the sp(3) hybridised nature of the coordinating nitrogens. These results show that the correlation between the (14)N hyperfine coupling and hybridisation of donor nitrogens can be useful to determine not only the coordination around the Cu(ii) metal centre but also the nature of the donor in unknown Cu(II) systems.