SYNTHESIS OF HYPERBRANCHED CONJUGATIVE POLY（ARYLENEETHYNYLENE）S BY ALKYNE POLYCYCLOTRIMERIZATION

A series of new hyperbranched poly(aryleneethynylene)s are synthesized by the copolycyclotrimerizations oftetraynes(Ⅰand Ⅱ)with aliphatic monoynes(A-C)catalyzed by tantalum-,niobium-,and cobalt-based catalysts.All thereactions proceed smoothly and soluble polymers of high molecular weights(M_w up to 3.8×10~4)are obtained in high yields(up to 97%).     

Catalytic asymmetric addition of alkylzinc and functionalized alkylzinc reagents to ketones

We describe our full report of the catalytic asymmetric addition of simple and functionalized dialkylzinc reagents to a broad range of saturated ketones and enones. The functionalized organozinc reagents contain esters, silyl ethers, alkyl chlorides, and alkyl bromides. In general, the resulting tertiary alcohol products are isolated with high ee's. With some substrates, yields are low as a result of the formation of aldol byproducts. Most substrates undergo additions with good yields reaching as high as 91%.     

Proton induced P-H and Mo-H bond activation at the phosphide bridged dimolybdenum complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4](R = Cy, 2,4,6-C6H2R'3; R'= H, Me, tBu)

The new hydride complexes [Mo2Cp2(mu-H)(mu-PHR)(CO)4] having bulky substituents (R = 2,4,6-C(6)H2tBu3= Mes*, R = 2,4,6-C6H2Me3= Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo2Cp2(CO)4] and further protonation of the resulting anionic phosphide complex [Mo2Cp2(mu-PHR)(CO)4]-. Protonation of the Mes* compound with either [H(OEt2)2][B{3,5-C6H3(CF3)2}4] or HBF4.OEt2 gives the cationic phosphinidene complex [Mo2Cp2(mu-H)(mu-PMes*)(CO)4]+ in high yield. In contrast, protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo2Cp2(mu-PHR)(CO)4]+, which are unstable at room temperature and display a cis geometry. Decomposition of the latter give the electron-precise pentacarbonyls [Mo2Cp2(mu-PHR)(mu-CO)(CO)4]+, also displaying a cis arrangement of the metal fragments. In the presence of BF4- as external anion, fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo2Cp2(mu-H)(mu-PFR)(CO)4]. Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus. In that case, using HCl as protonation reagent gave the chloro-complex [Mo2ClCp2(mu-PHPh)(CO)4] in good yield. The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and 1H, 31P, 19F and 13C NMR data as well as the X-ray studies carried out on [Mo2Cp2(mu-H)(mu-PHMes)(CO)4](cis isomer), [Mo2Cp2(mu-H)(mu-PFMes)(CO)4](trans isomer), [Mo2Cp2(mu-PHCy)(mu-CO)(CO)4](BF4) and [Mo2ClCp2(mu-PHPh)(CO)4].     

Synthesis and Crystal Structure of 1,7,7-Trimethyl- 4-（4-methoxyphenyl）-4,6,7,8-tetrahydroquinoline- 2,5（1H,3H）-diones under Microwave Irradiation

1 INTRODUCTION Various quinolone derivatives are known to dis- play interesting biological properties ranging from microbial activity to cytotoxicity[1]. They have been reported as antiviral (HIV-1)[2] and antitumor agents[3] as well as used as tubulin[4], topoisomerase[5] and thrombocyte inhibitors[6]. As a member of the quino- lone family, substituted N-phenyl-2-quinolones re-present the structural basis of many biologically active compounds, such as protein kinase inhibitors, immunodu…     

Photophysics and redox behavior of chiral transition metal polymers

The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)]](PF(6))(4) and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n) were shifted to lower energies and also exhibited significantly longer luminescence lifetimes when compared to [Ru((-)-ctpy)(2)](PF(6))(2), [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), and ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n). In terms of their electrochemical behavior, all of the complexes studied exhibited one Ru-centered and two ligand-centered redox waves and the [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n), and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n)() complexes were found to electrodeposit upon ligand-based reduction. The difference between the formal potentials of the Ru-centered and the first ligand-centered (least negative) waves corresponded linearly with the changes in the observed emission energies. The shifts in energy are discussed using a particle-in-a-box model, and the luminescence lifetimes are discussed in terms of the structure of the excited-state manifold.     

Flow injection determination of bismuth in urine by successive retention of Bi(III) and tetrahydroborate(III) on an anion-exchange resin and hydride generation atomic absorption spectrometry

Bismuth as BiCl₄⁻ and BH₄⁻ ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH₃). BiH₃ was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr₄⁻, BiI₄⁻ and BiCl₄⁻) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l⁻¹ of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l⁻¹. The R.S.D.% (n = 10) for a solution containing 50 μg l⁻¹ of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, and Mg²⁺. The most severe depression was caused by Hg²⁺, which at 60 mg l⁻¹ caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l⁻¹ could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l⁻¹ of Bi added to the samples prior to digestion with HNO₃ and H₂O₂ was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l⁻¹, respectively.     

Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates

Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra.