Bis(Diethyldithiocarbamato)Antimony(III) Derivatives with Oxygen- and Sulfur-Donor Ligands: Synthesis,Esi-Mass,and Spectral Characterization

Abstract

Replacement reactions of bis(diethyldithiocarbamato)antimony(III) chloride have been carried out with oxygen and sulfur donor ligands such as disodium oxalate, sodium acetate, sodium salicylate, benzoic acid, thioglycolic acid, acetylacetone, thiphenol, ethane-1,2-dithiol, and 2,2-dimethylpropane-1,3-diol to give mixed bis(diethyldithiocarbamato)antimony(III) derivatives of the corresponding ligands. These derivatives have been characterized by the physicochemical [melting point and molecular weight determination, elemental analysis (C, H, N, S, and Sb)], spectral [FT-IR, far-IR, NMR (¹H and ¹³C)], ESI-mass, powder XRD, and SEM studies.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables]     

An Allyl Uranium(IV) Sandwich Complex: Are ϕ Bonding Interactions Possible?

A method to explore head-to-head ϕ back-bonding from uranium f-orbitals into allyl π* orbitals has been pursued. Anionic allyl groups were coordinated to uranium with tethered anilide ligands, then the products were investigated by using NMR spectroscopy, single-crystal XRD, and theoretical methods. The (allyl)silylanilide ligand, N-((dimethyl)prop-2-enylsilyl)-2,6-diisopropylaniline (LH), was used as either the fully protonated, singly deprotonated, or doubly deprotonated form, thereby highlighting the stability and versatility of the silylanilide motif. A free, neutral allyl group was observed in UI₂(L1)₂ ( 1 ), which was synthesized by using the mono-deprotonated ligand [K][N-((dimethyl)prop-2-enyl)silyl)-2,6-diisopropylanilide] (L1). The desired homoleptic sandwich complex U[L2]₂ ( 2 ) was prepared from all three ligand precursors, but the most consistent results came from using the dipotassium salt of the doubly deprotonated ligand [K]₂[N-((dimethyl)propenidesilyl)-2,6-diisopropylanilide] (L2). This allyl-based sandwich complex was studied by using theoretical techniques with supporting experimental spectroscopy to investigate the potential for phi (ϕ) back-bonding. The bonding between U^IV and the allyl fragments is best described as ligand-to-metal electron donation from a two carbon fragment-localized electron density into empty f-orbitals.     

Patterned Monolayers of Neutral and Charged Functionalized Manganese Arene Complexes on a Highly Ordered Pyrolytic Graphite Surface

Complex patterns : The arene manganese tricarbonyl complexes [Mn(η⁵‐2,5‐didodecoxy‐1,4‐semiquinone)(CO)₃] and [Mn(η⁶‐1,4‐dioctyloxybenzene)(CO)₃] BF₄ form patterned monolayers on the surface of highly ordered pyrolytic graphite (HOPG), as a result of hydrogen‐bonding, hydrophobic, and electrostatic interactions, leading to an ordered 2D array of manganese atoms or ions.

     

K isomers in 254No: probing single-particle energies and pairing strengths in the heaviest nuclei

We have identified two isomers in 254No, built on two- and four-quasiparticle excitations, with quantum numbers K pi = 8- and (14+), as well as a low-energy 2-quasiparticle Kpi = 3+ state. The occurrence of isomers establishes that K is a good quantum number and therefore that the nucleus has an axial prolate shape. The 2-quasiparticle states probe the energies of the proton levels that govern the stability of superheavy nuclei, test 2-quasiparticle energies from theory, and thereby check their predictions of magic gaps.     

Validity of the Darwin and Ewald reflectivity functions in the range of the far wings: Neutron diffraction study

Using the neutron time-of-flight (TOF) technique, we have examined the reason for the dramatic departure of experimental results from the Darwin and Ewald reflectivity functions in the far wings. The scattering from Si(111) single- and triple-bounce crystals set up at the Bragg angle θB=24.4° was dispersed in time-of-flight in the wavelength range 0.3<λ<3.0 Å. The experiment reveals admixture of the single-scattered Bragg peaks and thermal diffuse scattering (TDS) originating at λ<0.6 Å in the spectrum registered from a triple-bounce crystal. Our study explains the discrepancy between the theory and the experimental results reported in many neutron studies and proves the validity of the Darwin and Ewald theories in the far wings.     

Aqueous RAFT Synthesis of Low Molecular Weight Anionic Polymers for Determination of Structure/Binding Interactions with Gliadin

Gliadin, a component of gluten and a known epitope, is implicated in celiac disease (CeD) and results in an inflammatory response in CeD patients when consumed. Acrylamide‐based polyelectrolytes are employed as models to determine the effect of molecular weight and pendent group on non‐covalent interaction modes with gliadin in vitro. Poly(sodium 2‐acrylamido‐2‐methylpropane sulfonate) and poly(sodium 3‐methylpropyl‐3‐butanoate) are synthesized via aqueous reversible addition fragmentation chain transfer (aRAFT) polymerization and characterized by gel permeation chromatography‐multiangle laser light scattering. The polymer/gliadin blends are examined via circular dichroism, zeta potential measurements, 8‐anilinonaphthalene‐1‐sulfonic acid fluorescence spectroscopy, and dynamic light scattering. Acrylamide polymers containing strong anionic pendent groups have a profound effect on gliadin secondary structure and solution behavior below the isoelectric point, while polymers containing hydrophobic character only have a minor impact. The polymers have little effect on gliadin secondary structure and solution behavior at the isoelectric point.     

Doorway states in the gamma decay-out of the yrast superdeformed band in 59Cu

The decay-out process of the yrast superdeformed band in 59Cu has been investigated. The firm determination of spin, parity, excitation energy, and configuration of the states involved in this process constitutes a unique situation for a detailed understanding of the decay-out mechanism. A theoretical model is introduced that includes a residual interaction and tunneling matrix element between bands, calculated in the configuration-dependent cranked Nilsson-Strutinsky model. This interaction causes the decay to occur via a small number of observed doorway states.     

E2 polarization charge in Sn

The nucleus ¹⁰²Sn, which is the lightest Sn isotope with known excited states, was investigated with the ⁵⁰Cr(⁵⁸Ni,α2n) reaction using delayed in-beam γ-ray and conversion-electron spectroscopy. The experimental setup was designed to study the decay of μs-long isomeric states by placing γ-ray and electron detectors behind the focal plane of the Fragment Mass Analyzer at the Argonne National Laboratory. A 44 keV conversion-electron line corresponding to the (6⁺)→(4⁺) transition in ¹⁰²Sn was identified and a half-life of 0.62^+0.43_−0.19 μs was measured for the (6⁺) state. From the available experimental information neutron effective charges from 1.6 to 2.3 e were deduced, based on the comparison with different shell-model calculations.     

Color-octet-electroweak-doublet scalars and the CDF dijet anomaly

We study the phenomenology of color-octet scalars in the (8,2)_1/2 representation in the context of the 3.2σ excess, in the dijet invariant mass spectrum of the W+jj final state, recently observed by the CDF Collaboration. We consider the region of parameter space with a sizable mass splitting between the charged and neutral color-octet scalars and consistent with electroweak precision data. We implement the principle of Minimal Flavor Violation (MFV) in order to suppress FCNC currents and reduce the number of free parameters. The excess in the W+jj channel corresponds to the charged current decay of the heavier neutral octet scalar into its lighter charged partner which decays into the two jets. In the MFV scenario, the production of the neutral color-octet is dominated by gluon fusion due to the Yukawa suppression of production via initial state quarks. As a result, no visible excess is expected in the γ+jj channel due to Yukawa and CKM suppression. Contributions to the Z+jj final state are suppressed for a mass spectrum where the decay of the heavier color-octet to this final state is mediated by an off-shell neutral color-octet partner. MFV allows one to control fraction of bottom quarks in the final state jets by a single ratio of two free parameters.     

Chemical and electrochemical reduction of polyarene manganese tricarbonyl cations: hapticity changes and generation of syn- and anti-facial bimetallic eta4,eta6-naphthalene complexes

(Eta6-naphthalene)Mn(CO)(3)(+) is reduced reversibly by two electrons in CH(2)Cl(2) to afford (eta4-naphthalene)Mn(CO)(3)(-). The chemical and electrochemical reductions of this and analogous complexes containing polycyclic aromatic hydrocarbons (PAH) coordinated to Mn(CO)(3)(+) indicate that the second electron addition is thermodynamically easier but kinetically slower than the first addition. Density functional theory calculations suggest that most of the bending or folding of the naphthalene ring that accompanies the eta6 --> eta4 hapticity change occurs when the second electron is added. As an alternative to further reduction, the 19-electron radicals (eta6-PAH)Mn(CO)(3) can undergo catalytic CO substitution when phosphite nucleophiles are present. Chemical reduction of (eta6-naphthalene)Mn(CO)(3)(+) and analogues with one equivalent of cobaltocene affords a syn-facial bimetallic complex (eta4,eta6-naphthalene)Mn(2)(CO)(5), which contains a Mn-Mn bond. Catalytic oxidative activation under CO reversibly converts this complex to the zwitterionic syn-facial bimetallic (eta4,eta6-naphthalene)Mn(2)(CO)(6), in which the Mn-Mn bond is cleaved and the naphthalene ring is bent by 45 degrees . Controlled reduction experiments at variable temperatures indicate that the bimetallic (eta4,eta6-naphthalene)Mn(2)(CO)(5) originates from the reaction of (eta4-naphthalene)Mn(CO)(3)(-) acting as a nucleophile to displace the arene from (eta6-naphthalene)Mn(CO)(3)(+). Heteronuclear syn-facial and anti-facial bimetallics are formed by the reduction of mixtures of (eta6-naphthalene)Mn(CO)(3)(+) and other complexes containing a fused polycyclic ring, e.g., (eta5-indenyl)Fe(CO)(3)(+) and (eta6-naphthalene)FeCp(+). The great ease with which naphthalene-type manganese tricarbonyl complexes undergo an eta6 --> eta4 hapticity change is the basis for the formation of both the homo- and heteronuclear bimetallics, for the observed two-electron reduction, and for the far greater reactivity of (eta6-PAH)Mn(CO)(3)(+) complexes in comparison to monocyclic arene analogues.