The Correspondence of Isaac Newton,Volume V, 1709–1713, edited by A. Rupert Hall and L. Tilling

This report reviews the recent progress that has been made toward understanding the necessary-for-life chemistry that took place on the prebiotic Earth, and that led to the appearance of the ht living cells. This understanding is based on the simulation, in the laboratory, of conditions analogous to those presumed (on geological and astronomical evidence), to have been present on the primitive Earth. Such research has led to the production of many of the classes of compounds that are key constituents of our contemporary biology. It has also led to the knowledge that abiogenetically produced organic compounds have an intrinsic tendency to assume the forms and the aggregations that are found in living cells. The report concludes with a summary of the exciting new finds of ‘biological’ molecules in interstellar space.     

Spectroscopic properties and quantum chemistry-based normal coordinate analysis (QCB-NCA) of a dinuclear tantalum complex exhibiting the novel side-on end-on bridging geometry of N2: correlations to electronic structure and reactivity

The vibrational properties and the electronic structure of the side-on end-on N(2)-bridged Ta complex ([NPN]Ta(micro-H))(2)(micro-eta(1):eta(2)-N(2)) (1) (where [NPN] = (PhNSiMe(2)CH(2))(2)PPh) are analyzed. Vibrational characterization of the Ta(2)(micro-N(2))(micro-H)(2) core is based on resonance Raman and infrared spectroscopies evaluated with a novel quantum chemistry-based normal coordinate analysis (QCB-NCA). The N-N stretching frequency is found at 1165 cm(-)(1) exhibiting a (15)N(2) isotope shift of -37 cm(-)(1). Four other modes of the Ta(2)N(2)H(2) core are observed between 430 and 660 cm(-)(1). Two vibrations of the bridging hydrido ligands are also identified in the spectra. On the basis of experimental frequencies and the QCB-NCA procedure, the N-N force constant is determined to be 2.430 mdyn A(-)(1). The Ta-N force constants are calculated to be 2.517 mdyn A(-)(1) for the Ta-eta(1)-N(2) bond and 1.291 and 0.917 mdyn A(-)(1) for the Ta-eta(2)-N(2) bonds, respectively. DFT calculations on 1 suggest that the bridging dinitrogen ligand carries a charge of -1.1, which is equally distributed over the two nitrogen atoms. However, orbital analysis reveals that the terminal nitrogen makes lower contributions to the pi orbitals and much higher contributions to the pi orbitals of the N(2) ligand than the bridging nitrogen. This suggests that reactions of the dinitrogen ligand with electrophiles should preferentially occur at the terminal N atom, in agreement with experimental results.     

Observation of slowed rotation about the (η6-arene)-chromium bond in the chromium tricarbonyl complex of thesyn-anti-syn trimer of bicyclo[2.2.1]hept-2-yne

Summary The crystal and molecular structures are reported for the chromium tricarbonyl complexes of the sterically-demanding and rigidsyn-anti-syn andall-syn trimers of bicyclo[2.2.1]hept-2-yne, (3-Cr) and (4-Cr). At very low temperatures, a decoalescence phenomenon occurs in the 75.49 MHz¹³C-{¹H}-NMR spectrum of (3-Cr) and is unambiguously assigned to slowed rotation about the (⁶-arene)-chromium bond.Dedicated to Professor Dr. Karl Schlögl on the occasion of his 65th birthday     

Local conserved charges in principal chiral models

We present a general construction of local, commuting conserved charges, with spins equal to the exponents, modulo the Coxeter number, of the underlying Lie algebra, for principal chiral models based on the classical Lie groups.     

Complete disassembly of carbon disulfide by a ditantalum complex

The side-on end-on dinitrogen complex [PhP(CH(2)SiMe(2)NPh)(2)Ta](μ-H)(2)(μ-η(2):η(1)-N(2)) reacts with CS(2) with complete cleavage of both C=S double bonds and the formation of [PhP(CH(2)SiMe(2)NPh)(2)Ta](μ-S)(2)(μ-CH(2)), which has two bridging sulfides and a bridging methylene unit. Further reaction with H(2) produces CH(4) and the disulfide complex.     

Application of Fenton‐Based Reactions for Treating Dye Wastewaters: Stability of Sulfonated Azo Dyes in the Presence of Iron(III)

Fenton‐ and photo‐assisted Fenton advanced oxidation processes generate reactive oxygen species from hydrogen peroxide and are candidates for the remediation of dye wastewaters. The purpose of this study was to investigate interactions of iron (III) with hydroxyazo dyes. The o‐hydroxyazo dyes Acid Orange 7 (AO7; 4‐[(2‐hydroxynaphthalen‐1‐yl)azo]benzenesulfonic acid sodium salt) and Acid Orange 10 (AO10; 7‐hydroxy‐8‐(phenylazo)naphthalene‐1,3‐disulfonic acid disodium salt) represent dyes allegedly able to chelate Fe^III through the chromophore. The p‐hydroxyazo dye Acid Orange 20 (AO20; 4‐[(4‐hydroxynaphthalen‐1‐yl)azo]benzenesulfonic acid sodium salt) represents an analogous structure that is unable to chelate Fe^III due to the position of the OH group. Reactions were carried out at pH 2 – 3 in perchlorate or chloride media in the absence of peroxide. No evidence was found by UV/VIS spectroscopy for complexation of Fe^III by the o‐hydroxyazo chromophore. Instead, Fe^III apparently coordinated or formed an ion pair with the sulfonate group, and, when only one sulfonate group was present (i.e., AO7), the dye formed a co‐precipitate with iron(III) hydrous oxides and perchlorate ion. Dye precipitation was seeded by colloidal iron hydrolysis product nuclei. By contrast, the p‐hydroxyazo dye (AO20) was rapidly oxidized by iron(III). The net Fe²⁺/oxidized AO20 ratio was 2 : 1, and a minor yield of 1,4‐naphthoquinone was obtained. The major initial oxidation product, which was not identified, formed a reversible complex with Fe²⁺. Results of this study indicate that the effectiveness of Fenton‐based methods for treating certain azo dyes that form insoluble ferric salts may be compromised by removal of the catalyst from solution. However, the degradation of certain other azo dyes might be assisted by direct thermal oxidation by iron(III).     

Portfolio Optimization With a Guaranteed Minimum Maturity Benefit and Risk-Adjusted Fees

Methodology and Computing in Applied Probability - We study a portfolio optimization problem involving the loss averse policyholder of a variable annuity with a guaranteed minimum maturity benefit....     

Enantioselective acylation using a second-generation P-aryl-2-phosphabicyclo[3.3.0]octane catalyst

The synthesis of P-aryl-2-phosphabicylco[3.3.0]octane x HBF4 salts 3a and 3c is described. Incorporation of the P-3,5-di-tert-butyl-4-methoxyphenyl group in 3c allows use of a less expensive aryl bromide starting material. Deprotonation of the air-stable salts in situ with triethylamine releases the corresponding phosphines 1a and 1c for use in the kinetic resolution of representative secondary alcohols. The method is convenient for small-scale experiments and affords enantioselectivities s close to the values obtained using the free phosphines 1a and 1b in cases where s is ca. 40 or lower.