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Tris(acenaphthyl)- and bis(acenaphthyl)-substituted pnictogens (iPr2P-Ace)3E (2-4) (E = As, Sb, or Bi; Ace = acenaphthene-5,6-diyl) and (iPr2P-Ace)2EPh (5 and 6) (E = As or Sb) were synthesized and fully characterized by multinuclear nuclear magnetic resonance (NMR), high-resolution mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. The molecules adopt propeller-like geometries with the restricted rotational freedom of the sterically encumbered iPr2P-Ace groups resulting in distinct NMR features. In the tris(acenaphthyl) species (2-4), the phosphorus atoms are isochronous in the 31P{1H} NMR spectra, and the rotation of the three acenaphthyl moieties around the E-Cipso bond is locked. On the other hand, the bis(acenaphthyl) species show a fluxional behavior, resulting in an AX to A2 spin system transition in the 31P{1H} variable-temperature NMR spectra. This allowed elucidation of remarkable through-space couplings (8TSJPP) of 11.5 Hz (for 5) and 25.8 Hz (for 6) at low temperatures. In addition, detailed line shape analysis of the thermodynamic parameters of the restricted rotation of the "propeller blades" in 5 was performed in the intermediate temperature region and also at coalescence. The lone pairs on the pnictogen atoms in 2-6 are oriented such that they form a bowl-shaped area that is somehow buried within the molecule.

Arsole-containing conjugated polymers are a practically unexplored class of materials despite the high interest in their phosphole analogues. Herein we report the synthesis of the first dithieno[3,2-b;2′,3′-d]arsole derivative, and demonstrate that it is stable to ambient oxidation in its +3 oxidation state. A soluble copolymer is obtained by a palladium-catalyzed Stille polymerization and demonstrated to be a p-type semiconductor with promising hole mobility, which was evaluated by field-effect transistor measurements.

Neutral inherently tri- and tetradentate ligands of the type Ph3-xAs(PyO)x (x = 2 (1), 3 (2)) have been synthesized and characterized. Reaction of 1 with [RuCl2(PPh3)3] affords complex [PhAs(μ-PyO)2RuCl2(PPh3)] (3), whereas 2 and [RuCl2(PPh3)3] react with formation of [As(μ-PyO)2RuCl(PPh3)2] (5) and [Ph3P(PyO)]Cl (6). Treatment of complex 5 with [AuCl(tht)] (tht = tetrahydrothiophene) results in liberation of tht and formation of [AuCl(As(PyO)2)RuCl(PPh3)2] (7), featuring an (Au-As-Ru) core. For compounds 3, 5, and 7 the As-Ru and As-Au bond situation has been investigated using NBO, AIM and ELF analysis, allowing the assignment of pronounced canonical forms of σ-(AsIII→RuII) to 3, σ-(AsII-RuI) to 5 and σ-(AuI←AsI→RuII) to 7. This journal is

Quternization of [chloro(phenyl)arsanyl]acetic acid with bromo- and iodoacetic acids in aqueous alkali follows SN2 mechanism and is accompanied by alkaline hydrolysis of haloacetic acids. The rate constants and thermodynamic parameters of the process were determined

A new clinical syndrome with prominent cerebellar symptoms in patients living in Kamisu City, Ibaraki Prefecture, Japan, is described. Since the patients ingested drinking water containing diphenylarsinic acid (DPA), a stable degradation product of both diphenylcyanoarsine and diphenylchloroarsine, which were developed for use as chemical weapons and cause severe vomiting and sneezing, DPA was suspected of being responsible for the clinical syndrome. The purpose of the present study was to elucidate prominent cerebellar symptoms due to DPA. The aim of the study was to determine if single (15 mg/kg) or continuous (5 mg/kg/day for 5 weeks) oral administration of DPA to ICR-strain mice induced oxidative and/or nitrosative stress in their brain. Significantly positive staining with malondialdehyde (MDA) and 3-nitrotyrosine (3-NT) was observed in the cerebellar Purkinje cells by repeated administration (5 mg/kg/day) with DPA for 5 weeks that led to the cerebellar symptoms from a behavioral pharmacology standpoint and by single administration of DPA (15 mg/kg). Furthermore, it is possible that the production of 3-NT was not caused by peroxynitrite formation. The present results suggest the possibility that arsenic-associated novel active species may be a factor underlying the oxidative and nitrosative stress in Purkinje cells due to exposure to DPA, and that the damage may lead to the cerebellar symptoms.

3-Arsolenes (R=Ph, Me, t-Bu, Cl, R'=H, Me) are readily obtained from zirconocene-butadiene complexes and RAsCl2.Alkylation with methyl iodide gives arsonium salts (R=Ph, Me, t-Bu, R'=H, Me), treatment with sulphur gives sulphides (R=Me, t-Bu), while oxidation with Br2 or SO2Cl2 results in ring cleavage.From chloroarsolene substitution products (R=I, H, SPh, OMe, NMe2) as well as coupling products with As-As, As-O-As, and As-S-As units were synthesized.In addition, a number of arsolene complexes with the metals chromium, molybdenum, tungsten, and ruthenium is described. Key words: Arsolene; Zirconocene; Group 6; Ruthenium; Phosphorus

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