SYNTHESES AND SPECTROSCOPIC PROPERTIES OF LANTHANIDE COMPLEXES, Ln(acac)_3(Ph_3PO)_3

A series of new complexes of formula Ln(acac)_s(Ph_3PO)_3 (where Ln~(3+)=Nd~(3+), Sm~(3+), Eu~(3+), Tb~(3+), Ho~(3+)) have been prepared and characterized. The coordination of two ligands with lanthanide ions are studied by IR spectra, ~1H, ~(13)C, ~(31)P-NMR and metal-ligand charge tranafer tranaition is also discussed via electronic adaorption and luminescence spectroscopy.     

New rhodium---ruthenium heterobimetallic complexes with bridging bi- or tri-dentate phosphine ligands

The mononuclear chelated complex [RuCl(Cp)(η²-dppa)] has been synthesised and reacted with [Rh₂Cl₂(CO)₄] to form the heterobimetallic complex [(Cp)Ru(μ-CO)₂{(μ-Ph₂PN(H)PPh₂}RhCl₂]. Complexes of [RuCl(Cp){(PPh₂)₂CHCH₂PPh₂}] have been reacted with [Rh₂Cl₂(CO)₄] or [RhCl(CO)₂(p-toluidene)]. Characterisation of these new ruthenium complexes was carried out using ³¹P-NMR, FAB mass spectroscopy, elemental analysis and IR spectrophotometry.     

Substituent Effects And Structure-Reactivity Relationship of Organophosphorus Compounds

To evaluate the substituent effect in organophosphorus compounds, a series of model compounds, namely 4-substituted-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octane-1-oxides, alkyl hydrogen p-substituted phenyl-phosphonates, dialkyl p-substituted phenylphosphonates, as well as alkyl hydrogen alkylphosphonates, were synthesized and studied. Since in these compounds the substituents are located far away from reaction centre and the contribution of the steric effect of substituents can thus be eliminated, the substituent polar effect was evaluated based on ³¹P NMR, pKa and charge density of phosphoryl oxygen of these compounds calculated by the quantum mechanies MNDO method. The results showed that the polar effects of substituent in carboxylic and organophosphorus esters are similar, and the variation in polar effect among the alkyl groups is not significant. In the meantime, some steric parameters E_s^p of substituents were suggested for organophosphorus compounds, which are different from the Taft's E_s and Charton's υ parameters^[1,2].     

Photocatalytic removal of the insecticide fenitrothion from water sensitized with TiO2

The photocatalytic removal of the insecticide fenitrothion (IUPAC name: O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), C₉H₁₂NO₅PS, from water suspension of TiO₂, was investigated by following the disappearance of the original substance along with the formation and disappearance of intermediates via recording NMR (¹H and ³¹P) and UV spectra, as well as by pH measurements. Based on the obtained data, a possible reaction mechanism was proposed. It was found that ³¹P-NMR spectrometry can be successfully used to follow the kinetics of transforming organic into inorganic phosphorus in the course of the degradation (k_a=9.2×10⁻⁷ mol dm⁻³ min⁻¹, r=0.980 for the illumination period after 15 h). The rate of fenitrothion aromatic ring decomposition was followed by UV spectrometry during the illumination (k_a=3.1×10⁻⁶ mol dm⁻³ min⁻¹, r=0.989). The complete mineralization was attained after about 66 h of irradiation.     

Rhenium(I) methoxo carbonyl complexes containing tetraphosphine or triphosphine ligands; facile separation and X-ray crystallographic studies of d/l- and meso-[{Re2(μ-OMe)2(CO)6}2(μ,μ′-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetra-phosphadecane)]

Reaction of the activated mixture of Re₂(CO)_10, Me₃NO and MeOH with a 1:1 mixture of rac (d/l)- and meso-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane (hptpd) yields a mixture of (d/l)- and meso-[{Re₂(μ-OMe)₂(CO)₆}₂(μ,μ′-hptpd)] 1. The diastereomers can be easily separated by selective dissolution of d/l-1 in benzene, and give clearly distinguishable ¹H- and ³¹P-NMR spectra. The fluxional behavior of d/l-1 in solution has been studied by variable-temperature ¹H- and ³¹P-{¹H}-NMR spectroscopy. The crystal structures of both d/l- and meso-1 have been determined. Both molecules consist of two {Re₂(μ-OMe)₂(CO)₆} moieties which are bridged by the two P---CH₂---CH₂---P moieties of the hptpd ligand. Whilst the molecules of meso-1 possess crystallographic i-symmetry, those of d/l-1 do not have any crystallographic symmetry. These diastereomers therefore give clearly distinguishable Raman spectra in the solid state. Reaction of tris[2-(diphenylphosphino)ethyl]phosphine (tdppep) with the activated mixture affords the complex [{Re₂(μ-OMe)₂(CO)₆}(μ,η²-tdppep)] 2, and the analogous reaction involving bis[2-diphenylphospinoethyl)phenylphosphine (triphos) gives [{Re₂(μ-OMe)₂(CO)₆}(μ,μ′,η³-triphos){Re₂(CO)₉}] 3 and [{Re₂(μ-OMe)₂(CO)₆}(μ,η²-triphos)] 4.     

Synthesis,structural characterization and solubility of 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3 -1,3,4-thiadiazolines

A series of novel 2-(1-substituted-1,11-undecylidene)-5-arylimino-△~3-1,3,4-thiadiazolines(4) were synthesized and their structure was characterized by ~1H NMR,~(13)C NMR and elemental analysis.Their solubility in both polar and non-polar solvents is significantly improved owing to the introduction of ethyl or methylthio group at cyclododecyl ring as compared with parent compounds[1,2-(1,11-undecylidene)-5-arylimino-△~3-1,3,4-miadiazolines].However,their fungicidal activity against Rhizoctonia solani is ...     

Formation of spiro and ansa derivatives in the reaction of 2,2,3,3,4,4-hexafluoropentane-1,5-diol with cyclotriphosphazene: Comparison with 2,2,3,3-tetrafluorobutane-1,4-diol

Reaction of cyclophosphazene, N₃P₃Cl₆ (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4-hexafluoropentane-1,5-diol (2), in THF solution at room temperature afforded five isolated products, whose structures have been characterised by X-ray crystallography and ¹H, ¹⁹F and ³¹P NMR spectroscopy: the mono-spiro compound, N₃P₃Cl₄(OCH₂CF₂CF₂CF₂CH₂O) (3), its ansa isomer (4), a di-spiro derivative N₃P₃Cl₂(OCH₂CF₂CF₂CF₂CH₂O)₂ (5), its spiro-ansa (6) isomer and the tri-spiro compound N₃P₃(OCH₂CF₂CF₂CF₂CH₂O)₃ (7). Quantitative ³¹P NMR measurements of the soluble portion of the reaction mixture show that in the reaction of (1) with the sodium derivative of the fluorinated pentanediol (2) there is a small preference for spiro compounds compared to ansa compounds (ratio ca. 1.3:1), similar to the analogous reaction of (1) with the sodium derivative of the fluorinated butanediol where there is a slightly greater proportion of spiro compared to ansa compounds (ratio ca. 1.5:1). The relative proportions of spiro and ansa compounds is likely to depend on the fine balance in stabilities of the different medium-sized rings in the fluorinated pentanediol (spiro, 8- and ansa, 10-membered rings) compared to the fluorinated butanediol (spiro, 7- and ansa, nine-membered rings) derivatives of cyclophosphazene.     

Reductive dehalogenation of chloro(alkynyl)phosphines by octacarbonyldicobalt

Reductive dehalogenation of the (chloro)(phenylethynyl)phosphine (2,4,6-^tBu₃C₆H₂O)(PhCC)PCl, I, by Co₂(CO)₈, II, yields the neutral phosphenium ion complex [(R)(R′)]P=Co(CO)₃, III, (R = 2,4,6-^tBu₃C₆H₂O; R′ = (η²-C≡CPh)Co₂(CO)₆), which contains a trigonally planar coordinated phosphorus atom. When NaCo(CO)₄, V, is used instead of II a dinuclear complex, Co₂(CO)₆[μ²-P(R)(R′)]₂, VI, (R = 2,4,6-^tBu₃C₆H₂O; R′ = C≡CPh) is formed in which the phosphido ligands P(R)(R′), bridge in a μ₂ fashion two Co(CO)₃ units. The mechanism of formation of VI, involving a formal dimerization of two [(2,4,6-^tBu₃C₆H₂O)(PhC≡C)]P=Co(CO)₃ fragments, is discussed. However, (^tBu)(PhC≡C)PCl, VII, reacts with II, to yield the cluster compound VIII, containing the two μ₂-bridging units (^tBu)[(η²-C≡CPh)Co₂(CO)₅]P and (^tBu)(PhC≡C)P.

Compounds II and VI–VIII were identified from their analytical and spectroscopic (IR, ¹H-, ¹³C- and ³¹P-NMR) data. The molecular structure of the cluster compound VIII was determined by an X-ray diffraction study.     

Solid-state static Cu and P CP/MAS NMR, and liquid-state EXAFS studies on copper(I) O,O′-dialkyldithiophosphate cluster compounds: Formation of the copper(I) O,O′-di-iso-amyldithiophosphate cluster compound on the surface of synthetic chalcocite

Polycrystalline octa-nuclear copper(I) O,O′-di-i-propyl- and O,O′-di-i-amyldithiophosphate cluster compounds, {Cu₈[S₂P(OR)₂]₆(μ₈-S)} where R = ⁱPr and ⁱAm, were synthesized and characterized by ³¹P CP/MAS NMR at 8.46 T and static ⁶⁵Cu NMR at multiple magnetic field strengths (7.05, 9.4 and 14.1 T). The symmetries of the electronic environments around the P sites were estimated from the ³¹P chemical shift anisotropy (CSA) parameters, δ_aniso and η. Analyses of the ⁶⁵Cu chemical shift and quadrupolar splitting parameters for these compounds are presented with the data being compared to those for the analogous octa-nuclear cluster compounds with R = ⁿBu and ⁱBu. The ⁶⁵Cu transverse relaxation for the copper sites in {Cu₈[S₂P(OⁱPr)₂]₆(μ₈-S)} and {Cu₈[S₂P(OⁱAm)₂]₆(μ₈-S)} was found to be very different, with a relaxation time, T₂, of 590 μs (Gaussian) and 90 μs (exponential), respectively. The structures of {Cu₄[S₂P(OⁱPr)₂]₄} and {Cu₈[S₂P(OⁱPr)₂]₆(μ₈-S)} cluster compounds in the liquid- and the solid-state were studied by Cu K-edge EXAFS. The disulfide, [S₂P(OⁱAm)₂]₂, was obtained and characterized by ³¹P{¹H} NMR. The interactions of the disulfide and of the potassium O,O′-di-i-amyldithiophosphate salt with the surfaces of synthetic chalcocite (Cu₂S) were probed using solid-state ³¹P NMR spectroscopy and only the presence of copper(I) dithiophosphate species with the {Cu₈[S₂P(OⁱAm)₂]₆(μ₈-S)} structure was observed.     

Synthesis and characterization of benzyl and benzoyl substituted oxime-phosphazenes

Two oxime-cyclophosphazenes were prepared from hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (7). The reactions of these oximes with benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride were studied. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with benzyl chloride (4) and benzoyl chloride, respectively. However, the oxime groups on 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride. Hexasubstituted compounds were also obtained from the reactions of hexakis(4-[(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) with benzoyl chloride (10), 4-methoxybenzoyl chloride (11) and 2-chlorobenzoyl chloride (12). A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride (9). All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy.     

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.     

New phosphabenzenes by [4 + 2] cycloaddition of stannoles to 1-phospha-1-alkynes — determination of signs of coupling constants [J(P, C), J(P, H), J(P, Si), J(Sn, P)]

Stannoles bearing dialkylboryl groups in 3-position react with 1-phospha-1-alkynes P≡C---^tBu (1) and P≡C---CH₂^tBu (2) by [4 + 2] cycloaddition and elimination of stannylene to give phosphabenzenes in high yield. The stannylenes oligomerise to give [R¹₂Sn]_n with n ≥ 7 (R --- Me, Et, -(CH₂)₅₋ or, in the case of R¹ = ^tBu, react with the stannole itself. All phosphabenzenes are characterized by their consistent sets of NMR data. The absolute signs of the coupling constants ⁿJ(³¹P, ¹H), ⁿJ(³¹P, ¹³C), ²J(³¹P, ²⁹Si) and ²J(¹¹⁹Sn, ³¹P) were determined by appropriate ID and 2D NMR experiments.     

Synthesis and X-ray crystal structures of [Ru4H4(CO) 11(PPh3)] and [Ru4−x IrxH2−x(CO) 12(PPh3) ] (x = 0 or 1)

Three tetranuclear clusters [Ru₄H₄(CO)₁₁(PPh₃)] (1), [Ru₄H₂(CO)₁₂(PPh₃)] (2) and [Ru₃IrH(CO)₁₂(PPh₃)] (3) were formed in the reaction of [Ir(CO)Cl(PPh₃)₂] and Na[Ru₃H(CO)₁₁] in tetrahydrofuran. Complexes 1–3 were characterized by IR and ¹H and ³¹P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls.     

高分辨NMR研究金属盐对水溶性铑膦配合物分子结构的影响

用高分辨NMR研究了NaCl、NiSO₄、CuSO₄、Fe₂(SO₄)₃和Cr₂(SO₄)₃对水溶性铑膦配合物HRh(CO)(TPPTS)₃[TPPTS;P(m-C₆H₄SO₃Na)₃]分子结构的影响.³¹P(¹H)和¹HNMR谱显示,于室温下在HRh(CO)(TPPTS)₃中加入的NaCl或NiSO₄对配合物的特征³¹P(¹H)和¹HNMR谱峰无明显影响;当加入CuSO₄后,配合物的Rh-H质子峰强度弱化明显,进而消失,且原配合物的特征磷谱峰强度减弱,新生成的磷物种谱峰逐渐成为磷谱的主要物种.当加入Fe₂(SO₄)₃或Cr₂(SO₄)₃后,三价金属离子的强顺磁性使NMR灵敏度下降,谱峰宽化,该2种盐均易与水溶性铑膦配合物产生强烈的相互作用,易使配合物特征谱峰消失.实验结果表明,上述金属盐对配合物结构破坏性大小的顺序为;Fe₂(SO₄)₃>Cr₂(SO₄)₃>CuSO₄》NiSO₄～NaCl.     

Effects of gamma irradiation on solid and lyophilised phospholipids

The effects of gamma irradiation (25 kGy) as a sterilisation method for phospholipids (distearoylphosphatidylcholine and distearoylphosphatidylglycerol) were investigated. ³¹P-NMR revealed minor chemical degradation of the phospholipids but lower dynamic viscosity and pseudoplasticity, lower turbidity, higher diffusion constant, smaller size, more negative zeta potential and changes in the phase transition behaviour of the subsequently produced liposomes were observed. The observed changes could to some extent be explained by the irradiation-induced degradation products (distearoylphosphatidic acid, fatty acids, lysophospholipids).     

Synthesis and spectroscopic properties of the novel cationic alkyne complexes [WI(CO)(NCMe)L2(η-RC2R)][BF4] (L = PEt3 or PMe2Ph; R = Me or Ph)

The complexes [WI₂(CO)L₂(η²-RC₂R)] (L = PEt₃ or PMe₂Ph; R = Me or Ph) react with an equimolar quantity of Ag[BF₄] in acetonitrile at room temperature to give good yields of the new purple cationic alkyne complexes [WI(CO)(NCMe)L₂(η²-RC₂R)][BF₄]. ³¹P NMR spectroscopy indicates that the phosphines are trans to each other in these compounds. ¹³C NMR spectroscopy suggests that the alkyne ligands are donating four electrons to the tungsten in these complexes.     

Gold(I) complexes with thiolate and triphenylphosphine ligands

The reaction of [AuCl(PPh₃)] with Pb(SR)₂(R = C₂H₅, C₆H₅, CH₂C₆H₅, C₆F₅, C₆H₂Me₃-2,4,6, Prⁱ and Bu^t) provides a clean method to obtain complexes of the type [Au(SR)(PPh₃)] in good yields. The new compounds have been characterized by IR, ¹H, ³¹P, ¹⁹F and ³¹C NMR. A study by FAB mass spectrometry indicates that an ion-molecule aggregation process takes place.     

Synthesis, characterization and some properties of novel bis(pentafluorophenyl)methoxyl substituted metal free and metallophthalocyanines

The preparation of some new tetrakis[bis(pentafluorophenyl)methoxyl] substituted metal free and metallophthalocyanine (MPcs) complexes were achieved by the tetramerization of 4-[bis(pentafluorophenyl)methoxy]phthalonitrile with Li metal in pentan-1-ol or metal [Co(II) or Zn(II)] acetates in DMAE, respectively. The structures of the target compounds were confirmed by elemental analysis, IR, UV–vis, ¹H NMR, ¹⁹F NMR and mass spectroscopic methods. MPcs are soluble only in strong and medium polar solvents while the metal free one is soluble in weakly, medium and strong polar solvents. The temperature and frequency dependence of the electrical conductivities were studied on spin coated films of the compounds using dc and impedance spectroscopy techniques in the frequency range from 40 to 10⁵ Hz and within the temperature range from 290 to 440 K. The temperature dependence of the exponent s and conductivity, σ_ac, were completely in agreement with the prediction of the hopping model. The redox properties of the complexes were determined by cyclic voltammetry. The nature of the redox processes was also confirmed using spectroelectrochemical measurements.     

1-Boraadamantane: reactivity towards mono-1-alkynyltin, -germanium and -silicon compounds — synthesis of 4-methylene-3-borahomoadamantanes

The reaction of 1-boraadamantane 1 with 1-alkynyltin (3), -germanium (4), and -silicon compounds (5) leads to enlargement of the tricyclic system by formation of 4-methylene-3-borahomoadamantanes (6–9). These are 1,1-organoboration reactions which proceed by cleavage of the M---C bond (M=Sn, Ge, Si). There is evidence for 1,1-deorganoboration which apparently take place much more readily than for non-cyclic analogues, most likely as the result of the strained tricyclic system. When 2-ethyl-1-boraadamantane (2) is used, again 3-borahomoadamantanes are formed, the isomers 15–18. The product distribution is sensitive to steric effects. However, it appears that the B---C(H)Et bond in 2 is slightly more reactive than the B---CH₂ bonds. All products were characterised by ¹H-, ¹¹B-, ¹³C-, ²⁹Si- and ¹¹⁹Sn-NMR.     

新型1,1-二氧代-4H-苯并[1,2,4]-噻二嗪类衍生物的合成及其抗肿瘤活性

以2-硝基苯磺酰氯为起始原料,经多步反应合成了12种新型1,1-二氧代-4H-苯并[1,2,4]-噻二嗪类衍生物,产物收率高,水溶性好,并经¹H NMR、¹³C NMR、MS-ESI和元素分析法确证结构。 用MTT法测试了这类衍生物对肝癌细胞HepG-2生长的抑制作用,结果显示目标化合物能不同程度地抑制肿瘤细胞生长,其中7-氨甲基-3-环丙基-1,1-二氧代-4H-苯并[1,2,4]-噻二嗪 (7c)对肝癌细胞HepG-2的抗性显著,最高抑制率达到79.3%。