2-Phospha-Allylic Systems

Abstract

Phosphamethincyanines prepared in 1964 by Dimroth and Hoffmann were among the first compounds with two-coordinate phosphorus. They are special cases of 2-phospha-allylic cations. Simple representatives of this type become available from the reaction of imidoyl chlorides with tris(trimethylsily1)phosphane.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Carbon dioxide induced separation of ionic liquids and water

Both hydrophobic and hydrophilic room-temperature ionic liquids can be separated from aqueous solutions with relatively low-pressure gaseous carbon dioxide.     

Highly stereoselective aldol reactions of titanium enolates from lactate-derived chiral ketones

[reaction: see text] Highly stereoselective titanium-mediated aldol reactions based on lactate-derived ketones are reported. The stereochemical outcome of the process depends on the protecting group (PMB or Bn) and the Lewis acid (i-PrOTiCl(3) or TiCl(4)) used in the enolization step, the corresponding anti-syn or syn-syn aldols being prepared in high yields and with diastereomeric ratios up to 99:1.     

IN VITRO STUDIES ON THE PHOTOSENSITIZED OXIDATION OF LENS PROTEINS BY PORPHYRINS

Abstract Porphyrins, which may be introduced into the eye as a result of abnormal porphyrin metabolism (uroporphyrin–Uro) or when used in the diagnosis or photodynamic therapy of certain tumors, including intraocular tumors (hematoporphyrin–Hp and'hematoporphyrin derivative'–Hpd and mesotetra( P -sulfonatophenyl)porphyrin–TPPS) are efficient photosensitizers in biological systems. We have been studying the potential phototoxic side effects of these drugs in the lens of the eye. Encapsulated in the human lens is a mixture of soluble protein crystallins. With little turnover of protein in the lens, any photosensitized modifications will accumulate and may result in an opacification of the lens. To evaluate the potential of different porphyrins to induce such damage, a series of porphyrins were photolyzed (transmission above 295 nm) in the presence of calf lens protein (2 mg m⁻¹). Marked photopolymerization and histidine destruction were observed for the lens protein photolyzed in the presence of all of the drugs. We have found that the relative effectiveness of the following porphyrins to induce that damage is: Uro = TPPS Hpd = Hp. Both the singlet oxygen quencher, azide, and the free radical scavenger, penicillamine, decrease this photosensitized oxidative damage to lens protein. TPPS binds significantly to lens protein and this binding leads to conformational changes in that protein.     

Synthesis,Characterisation, and in vitro Cytotoxic Activity of Dithiocarbamato Glycoconjugate Half-Sandwich Ruthenium and Osmium Complexes

The synthesis by transmetallation and in-depth characterisation by IR spectroscopy of five half-sandwich ruthenium and osmium dithiocarbamato isonipecotamide glycoconjugate complexes are presented herein. The evaluation of their in vitro cytotoxicity and of the zinc precursors’ in vitro cytotoxicity towards ovarian cancer (A2780 and A2780cisR) and normal prostate (PNT2) cells is reported. While the cytotoxicity of the compounds is rather limited, some selectivity is observed.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Two New Antiferromagnetic Nickel(II) Complexes Bridged by Azido Ligands in the Cis Position. Effect of the Counteranion on the Crystal Structure and Magnetic Properties

Two new nickel(II) end-to-end azido-bridged compounds, cis-catena-[NiL(2)(&mgr;-N(3))](n)()(ClO(4))(n)().nH(2)O (1) and [Ni(2)L(4)(&mgr;-N(3))(2)](PF(6))(2) (2), were synthesized and characterized; L is 2-(aminoethyl)pyridine. The crystal structures of 1 and 2 were solved. Complex 1: monoclinic system, space group P2(1)/a, a = 8.637(2) ?, b = 18.9995(7) ?, c = 12.3093(7) ?, beta = 105.92(2) degrees, Z = 4. Complex 2: triclinic system, space group P&onemacr;, a = 9.139(7) ?, b = 10.124(3) ?, c = 12.024(2) ?, alpha = 70.407(14) degrees, beta = 84.19(2) degrees, gamma = 67.67(4) degrees, Z = 1. In the two complexes the nickel atom is situated in a similarly distorted octahedral environment. The two complexes are different; 1 is a one-dimensional helicoidal complex with the two L ligands and the two end-to-end azido bridges in a cis arrangement while complex 2 is a dinuclear system with two end-to-end azido bridges, indicating the extreme importance of the counteranion present (ClO(4)(-) for 1 and PF(6)(-) for 2). The magnetic properties of the two compounds were studied by susceptibility measurements vs temperature. The chi(M) vs T plot for 1 shows the shape for a weakly antiferromagnetically coupled nickel(II) one-dimensional complex without a maximum until 4 K. In contrast, for complex 2 the shape of the chi(M) vs T curve shows a maximum near 40 K, indicating medium antiferromagnetic coupling. From the spin Hamiltonian -J(ij)()S(i)()S(j)(), J values for 1 and 2 were less than -1 and -29.1 cm(-)(1), respectively. The magnetic behavior for 1 and 2 may be explained in terms of the overlap between magnetic orbitals, taking into account the torsion of the Ni(II) atoms and azido-bridging ligands in the two structures.     

Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane

No Abstract     

Synthesis of tricyclic phospholene oxides by cycloaddition of phosphorus halides with heterocyclic analogs of 1-vinyl-3,4-dihydronaphthalenes

Replacement of C-4 with a hetero substituent (NR,O,S) in the 1-vinyl-3,4-dihydronaphthalene system has provided a new type of diene for participation in the McCormack cycloaddition reaction with P(III) halides. The tricyclic phospholene oxides so obtained are the first to bear an additional heteroatom in the ring system. 1,2-Dihydro-7-methoxy-1-(p-toluenesulfonyl)-4-vinylquinoline is a stable solid that reacts with methylphosphonous dichloride to give, after hydrolysis of the cycloadduct, the 1,2,4,5-tetrahydro-1H-phospholo-[2,3-c]quinoline ring system. The dihydroquinoline moiety was aromatized by detosylation with potassium t-butoxide. The tendency of 4-vinyl-2H-benzopyran to dimerize was a serious complication in its use, and the cycloaddition with methylphosphonous dichloride proceeded only in low yield. The product, a 2,3,3a,4-tetra-hydrobenzo[3,2-d]pyran derivative, was a stable, easily purified and characterized substance. 4-Vinyl-2H-benzo[b]thiopyran was more stable than the pyran, but the phospholo derivative from reaction with methylphosphonous dichloride was more difficult to purify. All products were characterized by ¹³C-nmr spectroscopy.