Revisiting Formal Copper(III) Complexes:Bridging Perspectives with <i>Quasi-d¹⁰</i> Configurations

The formal Cu(III) complex [Cu(CF(3))(4)](1−) has often served as a paradigmatic example of challenging oxidation state assignment – with many reports proposing conflicting descriptions. Here we report a computational analysis of this compound, employing Energy Decomposition Analysis and Intrinsic Bond Orbital Analysis. We present a quasi‐d ( 10 ) perspective of the metal centre, resulting from ambiguities in d‐electron counting. The implications for describing reactions which undergo oxidation state changes, such as the formal reductive elimination from the analogous [Cu(CF(3))(3)(CH(2)Ph)](1−) complex (Paeth et al. J. Am. Chem. Soc. 2019, 141, 3153), are probed. Electron flow analysis finds that the changes in electronic structure may be understood as a quasi‐d ( 10 ) to d ( 10 ) transition at the metal centre, rendering this process essentially redox neutral. This is reminiscent of a previously studied formal Ni(IV) complex (Steen et al., Angew. Chem. Int. Ed. 2019, 58, 13133–13139), and indicates that our description of electronic structure has implications for the understanding of elementary organometallic reaction steps

Homolytic X-H Bond Cleavage at a Gold(III) Hydroxide:Insights into One-Electron Events at Gold

C(sp(3))-H and O-H bond breaking steps in the oxidation of 1,4-cyclohexadiene and phenol by a Au(III)-OH complex were studied computationally. The analysis reveals that for both types of bonds the initial X-H cleavage step proceeds via concerted proton coupled electron transfer (cPCET), reflecting electron transfer from the substrate directly to the Au(III) centre and proton transfer to the Au-bound oxygen. This mechanistic picture is distinct from the analogous formal Cu(III)-OH complexes studied by the Tolman group (J. Am. Chem. Soc. 2019, 141, 17236-17244), which proceed via hydrogen atom transfer (HAT) for C-H bonds and cPCET for O-H bonds. Hence, care should be taken when transferring concepts between Cu-OH and Au-OH species. Furthermore, the ability of Au-OH complexes to perform cPCET suggests further possibilities for one-electron chemistry at the Au centre, for which only limited examples exist

Revisiting <i>sp²</i> Dilithio Methandiides:From Geometric Curiosity to Simple Bonding Description

The reported tetracoordinate dilithio methandiide complex from Liddle and co-workers (1) is investigated from a coordination chemistry perspective, to probe the origin of its intriguing geometry. Through the application of a variety of computational techniques, non-covalent (steric, electrostatic) interactions are found to be dominant. Further, we arrive at a bonding description which emphasizes the tricoordinate sp2-hybridized nature of the central methandiide carbon, differing somewhat from the original proposal. Thus, 1 is distinct from other dilithio methandiides since it contains only one C−Li σ-bond, and is found to be comparable to a simple aryllithium compound, phenyllithium.</p

Gold-Aluminyl and Gold-Diarylboryl Complexes:Bonding and Reactivity with Carbon Dioxide

The unconventional carbon dioxide insertion reaction of a gold-aluminyl [tBu3PAuAl(NON)] complex has been recently shown to be related to the electron-sharing character of the Au-Al bond that acts as a nucleophile and stabilizes the insertion product through a radical-like behavior. Since a gold-diarylboryl [IPrAuB(o-tol)2] complex with similar reactivity features has been recently reported, in this work we computationally investigate the reaction of carbon dioxide with [LAuX] (L = phosphine, N-heterocyclic carbene (NHC); X = Al(NON), B(o-tol)2) complexes to get insights into the Al/B anionic and gold ancillary ligand effects on the Au-Al/B bond nature, electronic structure, and reactivity of these compounds. We demonstrate that the Au-Al and Au-B bonds possess a similar electron-sharing nature, with diarylboryl complexes displaying a slightly more polarized bond as Au(δ+)-B(δ-). This feature reduces the radical-like reactivity toward CO2, and the Al/B anionic ligand effect is found to favor aluminyls over boryls, despite the greater oxophilicity of B. Remarkably, the ancillary ligand of gold has a negligible electronic trans effect on the Au-X bond and only a minor impact on the formation of the insertion product, which is slightly more stable with carbene ligands. Surprisingly, we find that the modification of the steric hindrance at the carbene site may exert a sizable control over the reaction, with more sterically hindered ligands thermodynamically disfavoring the formation of the CO2 insertion product

Exact General Relativistic Thick Disks

A method to construct exact general relativistic thick disks that is a simple generalization of the ``displace, cut and reflect'' method commonly used in Newtonian, as well as, in Einstein theory of gravitation is presented. This generalization consists in the addition of a new step in the above mentioned method. The new method can be pictured as a ``displace, cut, {\it fill} and reflect'' method. In the Newtonian case, the method is illustrated in some detail with the Kuzmin-Toomre disk. We obtain a thick disk with acceptable physical properties. In the relativistic case two solutions of the Weyl equations, the Weyl gamma metric (also known as Zipoy-Voorhees metric) and the Chazy-Curzon metric are used to construct thick disks. Also the Schwarzschild metric in isotropic coordinates is employed to construct another family of thick disks. In all the considered cases we have non trivial ranges of the involved parameter that yield thick disks in which all the energy conditions are satisfied.Comment: 11 pages, RevTex, 9 eps figs. Accepted for publication in PR

How reduced are nucleophilic gold complexes?

Nucleophilic formal gold(-i) and gold(i) complexes are investigated via Intrinsic Bond Orbital analysis and Energy Decomposition Analysis, based on density functional theory calculations. The results indicate gold(0) centres engaging in electron-sharing bonding with Al- and B- based ligands. Multiconfigurational (CASSCF) calculations corroborate the findings, highlighting the gap between the electonic structures and the oxidation state formalism

Reduction of myocardial infarction by postischemic administration of the calpain inhibitor A-705253 in comparison to the Na(+)/H(+) exchange inhibitor Cariporide (R) in isolated perfused rabbit hearts

The calpain inhibitor A-705253 and the Na(+)/H(+) exchange inhibitor Cariporide (R) were studied in isolated perfused rabbit hearts subjected to 60 min occlusion of the ramus interventricularis of the left coronary artery (below the origin of the first diagonal branch), followed by 120 min of reperfusion. The inhibitors were added to the perfusion fluid solely or in combination at the beginning of reperfusion. Hemodynamic monitoring and biochemical analysis of perfusion fluid from the coronary outflow were performed. Myocardial infarct size and area at risk (transiently not perfused myocardium) were determined from left ventricular slices after a special staining procedure with Evans blue and 2,3,5-triphenyltetrazolium chloride. The infarcted area (dead myocardium) was 72.7 +/- 4.0% of the area at risk in untreated controls, but was significantly smaller in the presence of the inhibitors. The largest effect was observed with 10(-6) M A-705253, which reduced the infarcted area to 49.2 +/- 4.1% of the area at risk, corresponding to a reduction of 33.6%. Cariporide (R) at 10(-6) M reduced the infarct size to the same extent. The combination of both inhibitors, however, did not further improve cardioprotection. No significant difference was observed between the experimental groups in coronary perfusion, left ventricular pressure, heart rate, or in the release of lactate dehydrogenase and creatine kinase from heart muscle

Exact General Relativistic Perfect Fluid Disks with Halos

Using the well-known ``displace, cut and reflect'' method used to generate disks from given solutions of Einstein field equations, we construct static disks made of perfect fluid based on vacuum Schwarzschild's solution in isotropic coordinates. The same method is applied to different exactsolutions to the Einstein'sequations that represent static spheres of perfect fluids. We construct several models of disks with axially symmetric perfect fluid halos. All disks have some common features: surface energy density and pressures decrease monotonically and rapidly with radius. As the ``cut'' parameter $a$ decreases, the disks become more relativistic, with surface energy density and pressure more concentrated near the center. Also regions of unstable circular orbits are more likely to appear for high relativistic disks. Parameters can be chosen so that the sound velocity in the fluid and the tangential velocity of test particles in circular motion are less then the velocity of light. This tangential velocity first increases with radius and reaches a maximum.Comment: 22 pages, 25 eps.figs, RevTex. Phys. Rev. D to appea

Vibrational properties of amorphous silicon from tight-binding O(N) calculation

We present an O(N) algorithm to study the vibrational properties of amorphous silicon within the framework of tight-binding approach. The dynamical matrix elements have been evaluated numerically in the harmonic approximation exploiting the short-range nature of the density matrix to calculate the vibrational density of states which is then compared with the same obtained from a standard O($N^4$) algorithm. For the purpose of illustration, an 1000-atom model is studied to calculate the localization properties of the vibrational eigenstates using the participation numbers calculation.Comment: 5 pages including 5 ps figures; added a figure and a few references; accepted in Phys. Rev.

Electrovacuum Static Counterrotating Relativistic Dust Disks

A detailed study is presented of the counterrotating model (CRM) for generic electrovacuum static axially symmetric relativistic thin disks without radial pressure. We find a general constraint over the counterrotating tangential velocities needed to cast the surface energy-momentum tensor of the disk as the superposition of two counterrotating charged dust fluids. We also find explicit expressions for the energy densities, charge densities and velocities of the counterrotating fluids. We then show that this constraint can be satisfied if we take the two counterrotating streams as circulating along electro-geodesics. However, we show that, in general, it is not possible to take the two counterrotating fluids as circulating along electro-geodesics nor take the two counterrotating tangential velocities as equal and opposite. Four simple families of models of counterrotating charged disks based on Chazy-Curzon-like, Zipoy-Voorhees-like, Bonnor-Sackfield-like and Kerr-like electrovacuum solutions are considered where we obtain some disks with a CRM well behaved. The models are constructed using the well-known ``displace, cut and reflect'' method extended to solutions of vacuum Einstein-Maxwell equations.Comment: 19 pages, 16 figures, revtex