Carbon-Centered Reactivity in Carbodiphosphorane-Based Ligands Allowing for Redox-Non-Innocent Ligand/Ligand Dual Bond-Activation.

A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive S.

1-Ethyl-3-methylimidazolium Acetate as a Reactive Solvent for Elemental Sulfur and Poly(sulfur nitride).

We investigate the reactive dissolution process of poly(sulfur nitride) (SN) in the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate [EMIm][OAc] in comparison to the process of elemental sulfur in the same IL. It has been known from the literature that during the reaction of S with [EMIm][OAc], the respective thione is formed via a radical mechanism. Here, we present new results on the kinetics of the formation of the respective imidazole thione (EMImS) via the hexasulfur dianion [S] and the trisulfur radical anion [S].

Characterization of the active site in the thiocyanate-forming protein from (TaTFP) using EPR spectroscopy.

Glucosinolates are plant thioglucosides, which act as chemical defenses. Upon tissue damage, their myrosinase-catalyzed hydrolysis yields aglucones that rearrange to toxic isothiocyanates. Specifier proteins such as thiocyanate-forming protein from (TaTFP) are non-heme iron proteins, which capture the aglucone to form alternative products, e.

Spectroscopic methods for assessing the molecular origins of macroscopic solution properties of highly concentrated liquid protein solutions.

In cases of subcutaneous injection of therapeutic monoclonal antibodies, high protein concentrations (>50 mg/ml) are often required. During the development of these high concentration liquid formulations (HCLF), challenges such as aggregation, gelation, opalescence, phase separation, and high solution viscosities are more prone compared to low concentrated protein formulations. These properties can impair manufacturing processes, as well as protein stability and shelf life.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO oxidation of a Mn(ii) precursor.

A unique trivalent manganese siloxide complex, blue-violet MnLiCl[(PhSiO)O](THF)·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (PhSiOH)O (1) followed by reaction with MnCl(THF) gave the structurally remarkable Mn(ii) precursor MnLiCl[(PhSiO)O](THF)·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO in THF to provide the Mn(iii) species 3 in high yield (91%).

Structure and reactivity of a mononuclear gold(II) complex.

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined.

Double quantum coherence ESR spectroscopy and quantum chemical calculations on a BDPA biradical.

Carbon-centered radicals are interesting alternatives to otherwise commonly used nitroxide spin labels for dipolar spectroscopy techniques because of their narrow ESR linewidth. Herein, we present a novel BDPA biradical, where two BDPA (α,α,γ,γ-bisdiphenylene-β-phenylallyl) radicals are covalently tethered by a saturated biphenyl acetylene linker. The inter-spin distance between the two spin carrier fragments was measured using double quantum coherence (DQC) ESR methodology.

Disupersilylperoxo radical anion [tBu3 SiOOSitBu3 ](⋅-) : an intermediate of supersilanide oxidation.

In the oxidative process of the supersilanide anion [SitBu3 ](-) , radical species are generated. The continuous wave (cw)-EPR spectrum of the reaction solution of Na[SitBu3 ] with O2 revealed a signal, which could be characterized as disupersilylperoxo radical anion [tBu3 SiOOSitBu3 ](⋅-) affected by sodium ions though ion-pair formation. A mechanism is suggested for the oxidative process of supersilanide, which in a further step can be helpful in a better understanding of the oxidation process of isoelectronic phosphanes.

The solvation study of carbon, silicon and their mixed nanotubes in water solution.

Nanotubes are believed to open the road toward different modern fields, either technological or biological. However, the applications of nanotubes have been badly impeded for the poor solubility in water which is especially essential for studies in the presence of living cells. Therefore, water soluble samples are in demand.

Solvation free energies of glutamate and its metal complexes: a computer simulation study.

Most biological ion channels demonstrate a high degree of selectivity for one type of ion more than others, and in many cases, how they control attaining this is still not clear. So we have studied on some metal ion compounds of glutamate. The Glutamate and its meal ion compounds (Ca(2+), Na(+), K(+) and Li(+)) were first modeled by ab initio calculations and then Monte Carlo simulation was used to calculate solvation free energies and also the complexes free energies for the related structures.