We herein report a computational study of the bonding in gold(I) vinylidene complexes and compare them to their carbene and CO analogues. The relevance of these intermediates is analysed for the ...intramolecular cyclisation leading to vinyl sulfonates.
During the past 10 years iron‐catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion Fe(CO)3(NO)−, which was originally described by Hogsed and ...Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with Fe(CO)42−, which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate Fe(CO)3(NO)− cannot be regarded as a Fe−II species, but rather is predominantly a Fe0 species, in which the metal is covalently bonded to NO− by two π‐bonds. A metal–N σ‐bond is not observed.
Even more complex: Spectroscopic and quantum chemical investigations show that the complex ferrate Fe(CO)3(NO)− cannot be considered to be a Fe−II species, but rather is predominantly an Fe0 species, in which the metal is covalent bound to NO− by two π bonds. A metalN σ bond is not observed.
The potential of vinyl Au species to react either through a controlled π‐ or σ‐pathway is demonstrated. This nomenclature is directly derived from the orbitals of the vinyl Au species leading to the ...newly formed bonds. When the π‐bond of the vinyl Au intermediate is transformed into a σ‐bond, we name it π‐pathway, and a σ‐ to σ‐ transformation is named σ‐pathway. Examples of reactions following these pathways are a Au‐catalysed 3,3‐sigmatropic rearrangement and a protodeauration reaction. These reactions have been studied using intrinsic bond orbitals (IBOs) and allow for the clear identification of these pathways. Energies for the reaction path of the Au‐catalysed 3,3‐sigmatropic rearrangement were in addition computed using CCSD(T)‐F12. Analysis of the intrinsic reaction coordinate (IRC) of the 3,3‐sigmatropic rearrangement using IBOs further allows us to refine the previous mechanistic proposal and identifies a hidden intermediate along the reaction path.
One intermediate, two reaction channels: Following the intrinsic reaction coordinates of a Au‐catalysed sigmatropic rearrangement and a protodeauration reaction, two different reaction pathways were found aided by intrinsic bond orbital analysis, showing the versatility of vinyl gold species in the context of catalysis.
The spin chemistry of photoinduced charge-separated (CS) states of three triads comprising one or two triarylamine donors, a cyclometalated iridium complex sensitizer and a naphthalene diimide (NDI) ...acceptor, was investigated by transient absorption spectroscopy in the ns−μs time regime. Strong magnetic-field effects (MFE) were observed for two triads with a phenylene bridge between iridium complex sensitizer and NDI acceptor. For these triads, the lifetimes of the CS states increased from 0.6 μs at zero field to 40 μs at about 2 T. Substituting the phenylene by a biphenyl bridge causes the lifetime of the CS state at zero field to increase by more than 2 orders of magnitude (τ = 79 μs) and the MFE to disappear almost completely. The kinetic MFE was analyzed in the framework of a generalized Hayashi–Nagakura scheme describing coherent (S, T0 ↔ T±) as well as incoherent (S, T0 ⇌ T±) processes by a single rate constant k ±. The magnetic-field dependence of k ± of the triads with phenylene bridge spans 2 orders of magnitude and exhibits a biphasic behavior characterized by a superposition of two Lorentzians. This biphasic MFE is observed for the first time and is clearly attributable to the coherent (B < 10 mT) and incoherent (10 mT < B < 2 T) domains of spin motion induced by isotropic and anisotropic hyperfine coupling. The parameters of both domains are well understood in terms of the structural properties of the two triads, including the effect of electron hopping in the triad with two donor moieties. The kinetic model also accounts for the reduction of the MFE on reducing the rate constant of charge recombination in the triad with the biphenyl bridge.
Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of -2 at a transition-metal center. For a series of formal high-valent Ni
complexes, ...aryl-CF
bond-forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034-8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal Ni
centers are better described as approaching a +II oxidation state, originating from highly covalent metal-ligand bonds, a phenomenon attributable to σ-noninnocence. A direct consequence is that the elimination of aryl-CF
products occurs in an essentially redox-neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF
group is transferred to an electrophilic aryl group. The uncovered role of σ-noninnocence in metal-ligand bonding, and of an essentially redox-neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.
OBJECTIVEWe sought to identify motor features that would allow the delineation of individuals with sleep study-confirmed idiopathic REM sleep behavior disorder (iRBD) from controls and Parkinson ...disease (PD) using a customized smartphone application.
METHODSA total of 334 PD, 104 iRBD, and 84 control participants performed 7 tasks to evaluate voice, balance, gait, finger tapping, reaction time, rest tremor, and postural tremor. Smartphone recordings were collected both in clinic and at home under noncontrolled conditions over several days. All participants underwent detailed parallel in-clinic assessments. Using only the smartphone sensor recordings, we sought to (1) discriminate whether the participant had iRBD or PD and (2) identify which of the above 7 motor tasks were most salient in distinguishing groups.
RESULTSStatistically significant differences based on these 7 tasks were observed between the 3 groups. For the 3 pairwise discriminatory comparisons, (1) controls vs iRBD, (2) controls vs PD, and (3) iRBD vs PD, the mean sensitivity and specificity values ranged from 84.6% to 91.9%. Postural tremor, rest tremor, and voice were the most discriminatory tasks overall, whereas the reaction time was least discriminatory.
CONCLUSIONSProdromal forms of PD include the sleep disorder iRBD, where subtle motor impairment can be detected using clinician-based rating scales (e.g., Unified Parkinsonʼs Disease Rating Scale), which may lack the sensitivity to detect and track granular change. Consumer grade smartphones can be used to accurately separate not only iRBD from controls but also iRBD from PD participants, providing a growing consensus for the utility of digital biomarkers in early and prodromal PD.
We provide an investigation of the charge carrier dynamics of the (MAI)(x)(PbI2)(1-x) system in the range x = 0.32-0.90 following the recently published "pseudobinary phase-composition processing ...diagram" of Song et al. (Chem. Mater., 2015, 27, 4612). The dynamics were studied using ultrafast pump-supercontinuum probe spectroscopy over the pump fluence range 2-50 μJ cm(-2), allowing for a wide variation of the initial carrier density. At high MAI excess (x = 0.90), low-dimensional perovskites (LDPs) are formed, and their luminescence spectra are significantly blue-shifted by ca. 50 nm and broadened compared to the 3D perovskite. The shift is due to quantum confinement effects, and the inhomogeneous broadening arises from different low-dimensional structures (predominantly 2D, but presumably also 1D and 0D). Accurate transient carrier temperatures are extracted from the transient absorption spectra. The regimes of carrier-carrier, carrier-optical phonon and acoustic phonon scattering are clearly distinguished. Perovskites with mole fractions x ≤ 0.71 exhibit extremely fast carrier cooling (ca. 300 fs) at low fluence of 2 μJ cm(-2), however cooling slows down significantly at high fluence of 50 μJ cm(-2) due to the "hot phonon effect" (ca. 2.8 ps). A kinetic analysis of the electron-hole recombination dynamics provides second-order recombination rate constants k2 which decrease from 5.3 to 1.5 × 10(-9) cm(3) s(-1) in the range x = 0.32-0.71. In contrast, recombination in the LDPs (x = 0.90) is more than one order of magnitude faster, 6.4 × 10(-8) cm(3) s(-1), which is related to the confined perovskite structure. Recombination in these LDPs should be however still slow enough for their potential application as efficient broadband emitters or solar light-harvesting materials.
1,4-Cyclohexadiene (CHD) and 9,10-dihydroanthracene (DHA) are two substrates used to probe the steric requirements of metal-oxo oxidants in H-atom-transfer (HAT) reactions, based on the assumption ...that they have comparable C-H bond dissociation enthalpies (BDEs). We use computations to demonstrate that the BDE of DHA is ∼3.5 kcal mol(-1) larger than that of CHD and that their often comparable reactivity is based on a competing interplay of bond strengths and favorable van der Waals interactions.
The base metal complex Bu4NFe(CO)3(NO) (TBAFe) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or ...aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the Fe(CO)3(NO) anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial pi -complex with the incoming organic substrate.