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The electronic nature of Ni π‐complexes is underexplored even though these complexes have been widely postulated as intermediates in organometallic chemistry. Herein, the geometric and electronic structure of a series of nickel π‐complexes, Ni(dtbpe)(X) (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane; X=alkene or carbonyl containing π‐ligands), is probed using a combination of 31P NMR, Ni K‐edge XAS, Ni Kβ XES, and DFT calculations. These complexes are best described as square planar d10 complexes with π‐backbonding acting as the dominant contributor to M−L bonding to the π‐ligand. The degree of backbonding correlates with 2JPP from NMR and the energy of the Ni 1s→4pz pre‐edge in the Ni K‐edge XAS data, and is determined by the energy of the π*ip ligand acceptor orbital. Thus, unactivated olefinic ligands tend to be poor π‐acids whereas ketones, aldehydes, and esters allow for greater backbonding. However, backbonding is still significant even in cases in which metal contributions are minor. In such cases, backbonding is dominated by charge donation from the diphosphine, which allows for strong backdonation, although the metal centre retains a formal d10 electronic configuration. This ligand‐induced backbonding can be formally described as a 3‐centre‐4‐electron (3c‐4e) interaction, in which the nickel centre mediates charge transfer from the phosphine σ‐donors to the π*ip ligand acceptor orbital. The implications of this bonding motif are described with respect to both structure and reactivity. Backbonding like never before: A series of Ni π‐complexes were explored using a combination of spectroscopic and computational methods to reveal an intriguing contribution to backbonding: metal‐mediated ligand‐to‐ligand backdonation. Such ligand‐induced backdonation is the dominant contribution for weakly π‐acidic ligands such as alkenes and allows for strong bonding while retaining a formal d10 electronic configuration. [ABSTRACT FROM AUTHOR]

Electron paramagnetic resonance was used in conjunction with X-ray fluorescence spectroscopy to quantify total copper and reacted copper retentions in MCQ and MCA treated Canadian red pine sapwood and western hemlock heartwood. Total copper retentions were distinctly different between earlywood and latewood of both softwood species examined. Earlywood of red pine sapwood had higher total copper content than the latewood, while western hemlock heartwood had higher total copper contents in latewood than earlywood. The reacted copper concentrations were similar in earlywood and latewood, reflecting a similar capacity of each to solubilize and complex the reacted copper. [ABSTRACT FROM AUTHOR]

Sapwood sawdust from southern pine was treated with micronized copper (MC) under various conditions and the mobilized copper(II) (Cumob) concentrations were determined in the treated wood by electron paramagnetic resonance (EPR) spectroscopy. The spectral parameters for the copper sulfate (CuSO4)-treated sapwood and those of the MC-treated sapwood were very similar. A linear correlation was found between the intensities of copper (Cu) EPR spectra and those of Cu energydispersive X-ray fluorescence spectroscopy in a series of CuSO4-treated sapwood reference samples. Thus, the EPR signal intensities could be reliably correlated to the mass of reacted Cu present using this calibration curve. The amount of the Cumob in sawdust treated by MC suspensions increased during the first 2-3 days after the initial treatment and then reached a maximum during the 7-day monitoring period. In the case of the treatment with MC alone or MC azole, an increased MC concentration led to an elevated amount of Cu (to a maximum of ~0.23% Cu) solubilized by the sapwood. If the wood was treated with MC quat, the Cumob initially increased, but at higher concentrations the Cumob content decreased, due to the interference by the quat cobiocide on the acid reaction between the wood and the basic Cu carbonate. An examination of commercially-treated wood confirmed the laboratory observations. [ABSTRACT FROM AUTHOR]

Sulfur K-edge X-ray absorption spectroscopy (S K-edge XAS) was applied to investigate the electronic structure of primary and tertiary S-nitrosothiols. Our experimental data, supported by density functional calculations, indicate that changes at Cα affect the S-nitroso group through both inductive and direct orbital effects. Furthermore, our data are consistent with a weakening of the S-N bond in tertiary S-nitrosothiols as compared to their primary S-nitroso analogues. These results support existing computational models and suggest that the reactivity of S-nitrosothiols is not dominated by the electronics of the S-N bond. On a fait appel à la spectroscopie d'absorption des rayons-X près du seuil K du soufre (SAX près du seuil K du soufre) pour étudier la structure électronique de S-nitrothiols primaires et tertiaires. Les données expérimentales et les calculs de la fonctionnelle de la densité indiquent que les changements au niveau du Cα affectent le groupe S-nitroso par des effets inductifs ainsi que par des effets directs d'orbitales. De plus, les données sont en accord avec un affaiblissement de la liaison S-N dans les S-nitrosothiols primaires par rapport à leurs analogues S-nitroso primaires. Ces résultats supportent les modèles existants dérivés de calculs théoriques et ils suggèrent que la réactivité des S-nitrosothiols n'est pas dominée par les effets électroniques de la liaison S-N. [ABSTRACT FROM AUTHOR]

Despite a wealth of studies exemplifying the utility of the 2-5 keV X-ray range in speciation and electronic structure elucidation, the exploitation of this energy regime for the study of photochemical processes has not been forthcoming. Herein, a new endstation set-up for in situ photochemical soft X-ray spectroscopy in the 2-5 keV energy region at the Stanford Synchrotron Radiation Lightsource is described for continuous photolysis under anaerobic conditions at both cryogenic and ambient temperatures. Representative examples of this approach are used to demonstrate the potential information content in several fields of study, including organometallic chemistry, biochemistry and materials chemistry. [ABSTRACT FROM AUTHOR]

The photochemistry of methionine, methionine sulfoxide, and methionine sulfone have been investigated by using sulfur K-edge X-ray absorption spectroscopy to explore the redox photochemical processes under different conditions. Methionine is easily photooxidized to the sulfoxide and the sulfone in the presence of dioxygen. In the absence of oxidant, photoirradiation leads to the one-electron-oxidized cation radical with no further reaction, suggesting that an alternative mechanism for photooxidation of thioethers through direct oxidation is feasible. The photochemistry of methionine sulfoxide allows for independent oxidative and reductive processes. Photoreduction of the sulfoxide leads back to the parent thioether under both aerobic and anaerobic conditions. Photooxidation occurs only under aerobic conditions. In contrast, methionine sulfone is photochemically inert. These results provide new insights into potential photochemical processes that may lead to cataract formation. [ABSTRACT FROM AUTHOR]

The article presents a study on electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis. It focuses on the use of element-specific X-ray spectroscopies with electronic structure calculations to probe bonding, measure electronic contributions to reactivity and determine the influence of certain catalyst modifications. It determines the electronic effect of PR3 and N-heterocyclic carbenes litigation on the metal center to address kinetic differences.