首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
The thermal reaction of Ru3(CO)12 with the biologically active acids acetyl salicylic acid (Aspirin), α-methyl-4-(isobutyl)phenylacetic acid (Ibuprofen) and 3α,7α,12α-trihydroxy-5β-cholanic acid (cholic acid) in refluxing tetrahydrofuran, followed by addition of triphenylphosphine, gives the dinuclear complexes Ru2(CO)4(OOCR)2(PPh3)2 (1: R = C6H4-2-OCOMe, 2: R = CHMe-C6H4-4-Bui, 3: C23H39O3). The single-crystal structural analysis of 1 and 2 reveals a dinuclear Ru2(CO)4 sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two phosphine ligands occupy the axial positions at the ruthenium atoms. However, chiral carbon atoms in the carboxylic acid undergo racemisation during the thermal reaction.  相似文献   

2.
Rat corpus striatum contained α2-adrenergic receptor which were labelled with [3H]clonidine (95 ± 6 fmol/mg protein). The affinity of these receptors (Kd = 1.3 to 3.6 nM) was similar to that found in cerebral cortex. Five days after kainic lesions, the number of α2-adrenergic receptors had dropped by half, suggesting that their location might be neuronal. One month after lesions, the number of α2-adrenergic receptors had risen to that of the controls and was higher after two months. This increase would suggest a glial localization of the α2-adrenergic receptor. We have previously described the presence of α2-adrenergic receptors in primary astrocyte cultures (Ebersolt et al., 1981). Rat corpus striatum contained less α1-adrenergic receptors than α2-adrenergic receptors. They were labelled with [3H]prazosin (28 ± 1.9 fmol/mg protein) and were only slightly altered 5 days after kainic acid lesions (?20%). In addition to these classical α1-adrenergic receptors, rat corpus striatum also contained [3H]WB4101 binding sites having high affinity for WB4101 (2–5 nM) and norepinephrine (1 μM) but a very low affinity for prazosin (4.4 μM). The exact nature of these sites remains unknown.  相似文献   

3.
Reactions of [Pt2(μ-S)2(PPh3)4] with the diarylthallium(III) bromides Ar2TlBr [Ar = Ph and p-ClC6H4] in methanol gave good yields of the thallium(III) adducts [Pt2(μ-S)2(PPh3)4TlAr2]+, isolated as their salts. The corresponding selenide complex [Pt2(μ-Se)2(PPh3)4TlPh2]BPh4 was similarly synthesised from [Pt2(μ-Se)2(PPh3)4], Ph2TlBr and NaBPh4. The reaction of [Pt2(μ-S)2(PPh3)4] with PhTlBr2 gave [Pt2(μ-S)2(PPh3)4TlBrPh]+, while reaction with TlBr3 gave the dibromothallium(III) adduct [Pt2(μ-S)2(PPh3)4TlBr2]+[TlBr4]. The latter complex is a rare example of a thallium(III) dihalide complex stabilised solely by sulfur donor ligands. X-ray crystal structure determinations on the complexes [Pt2(μ-S)2(PPh3)4TlPh2]BPh4, [Pt2(μ-S)2(PPh3)4TlBrPh]BPh4 and [Pt2(μ-S)2(PPh3)4TlBr2][TlBr4] reveal a greater interaction between the thallium(III) centre and the two sulfide ligands on stepwise replacement of Ph by Br, as indicated by shorter Tl-S and Pt?Tl distances, and an increasing S-Tl-S bond angle. Investigations of the ESI MS fragmentation behaviour of the thallium(III) complexes are reported.  相似文献   

4.
The α3β1integrin has been implicated as a receptor for several matrix components, including collagen, fibronectin, and laminins. The function of α3β1seems to be very versatile involving cell adhesion to or migration on ECM, establishment of cell–cell contacts in aggregates, as well as linkage to intracellular tyrosine phosphorylation cascades. Here we report a strong induction of attachment of α3β1integrin expressing human breast carcinoma cell line MDA MB 231 to matrix proteins by two α3integrin subunit function-blocking monoclonal antibodies (P1B5 and ASC-1). In contrast, stimulation of adhesion to ECM by inhibitory α3integrin-specific antibodies was not observed in the α3β1integrin-expressing nonmalignant human mammary epithelial cell line MCF-10A or the human breast carcinoma cell line MDA MB 468 that expressed relatively low amounts of α3β1integrin at the cell surface. This increase was specific for collagens and not observed on fibronectin or laminin. Physiological concentrations of bivalent cations were not required. MAb P1B5 did not induce homotypic aggregation of MDA MB 231 cells. The P1B5-induced increase in cell attachment to collagens could be prevented but not reduced below control levels by blocking mAb to the α2integrin subunit. Function blocking anti-α5integrin subunit mAb was without effect while anti-β1-mAb completely abolished adhesion. Our data indicate that negative cooperativity between integrins results in transdominant inhibition of α2β1function by α3β1in human MDA MB 231 but not MDA MB 468 tumor cells or nonmalignant MCF-10A cells.  相似文献   

5.
Two novel tetranuclear compounds with an unprecedented mode of a hydrogenphosphato bridge, [Cu4(dpyam)443-HPO4)2(μ-X)2]2+ (in which dpyam = di-2-pyridylamine and X = Cl (1), Br (2)) have been synthesised and characterised structurally and magnetically. The Cu(II) ions in the structures each display a square-pyramidal geometry, with two tridentate hydrogenphosphato groups bridging four copper atoms in a μ43 coordination mode which is rarely found in hydrogenphosphate metal compounds. Each (different) pair of Cu(II) ions is additionally bridged by halide ions, with relatively long Cu-X distances (2.551(3)-2.604(3) Å for 1 and 2.707(1)-2.766(2) Å for 2) and subsequently also a small Cu-X-Cu angle (65.7(1)° and 65.1(1)° for 1 and 61.6(1)° and 62.4(1) for 2) and a large Cu-X-Cu angle (95.5(1)° and 96.5(1)° for 1 and 91.1(1)° and 92.6(1)° for 2). Cu?Cu distances in the tetranuclear units varies from 2.802(3) to 5.232(3) Å for 1 and from 2.834(1) to5.233(1) Å in 2. The lattice structures are stabilised by extensive intermolecular hydrogen bonds. The magnetic susceptibility measurements down to 5 K revealed a weak ferromagnetic interaction between the outer pairs of Cu(II) ions which vary from 22 to 46 cm−1 in 1 and 12 to 33 cm−1 in 2 and a moderately strong antiferromagnetic interaction between the inner Cu(II) ions of −79 cm−1 in 1 and −83 cm−1 in 2, via the Cu-O-P-O-Cu pathway.  相似文献   

6.
The [Co2(CO)6(RC2R′)] complexes (R, R′ = H, Me, Et, Prn) react with molecular hydrogen under mild conditions of temperature and pressure, at low but appreciable rates. The effect of the steric hindrance of the substituents and the strength of the metalcarbon bonds are discussed. The kinetic data measured for [Co2(CO)6(HC2H)], suggest that both H2-coordination and CO-dissociation are involved in the rate-determining step of the overall hydrogenation process.The catalytic activity of [Co2(CO)6(HC2H)] in the homogeneous hydrogenation of acetylene is described. At low substrate/catalyst ratio the initial hydrogenation rate is equal, within experimental error, to that found for the stoichiometric reaction; on increasing the acetylene concentration, cyclotrimerization to benzene becomes the dominant process. Interestingly C4 hydrocarbons (mainly butadiene and 1-butene) are produced in measurable yield (?8%). The formation of these products is interpreted as the result of the hydrogenation of the elusive [Co2(CO)5(HC2H)2] complex, an unstable intermediate in the cyclotrimerization chain.  相似文献   

7.
Routes to the synthesis of the mixed sulfide-phenylthiolate complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ have been explored; reaction of [Pt2(μ-S)2(PPh3)4] with excess Ph2IBr proceeds readily to selectively produce this complex, which was structurally characterised as its PF6 salt. Reactions of [Pt2(μ-S)2(PPh3)4] with other potent arylating reagents (1-chloro-2,4-dinitrobenzene and 1,5-difluoro-2,4-dinitrobenzene) also produce the corresponding nitroaryl-thiolate complexes [Pt2(μ-S){μ-SC6H2(NO2)2X}(PPh3)4]+ (X = H, F). The complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ reacts with Me2SO4 to produce the mixed alkyl/aryl bis-thiolate complex [Pt2(μ-SMe)(μ-SPh)(PPh3)4]2+, but corresponding reactions with the nitroaryl-thiolate complexes are plagued by elimination of the nitroaryl group and formation of [Pt2(μ-SMe)2(PPh3)4]2+. [Pt2(μ-S)(μ-SPh)(PPh3)4]+ also reacts with Ph3PAuCl to give [Pt2(μ-SAuPPh3)(μ-SPh)(PPh3)4]2+.  相似文献   

8.
The reduction of ethanolic solutions of niobium pentachloride with zinc, followed by treatment with aqueous acids serves as a versatile entry into the aqueous solution chemistry of niobium. From the zinc-reduced solution, the major intermediate, Nb42-O)22-OC2H5)4Cl4(OC2H5)4(HOC2H5)4, was isolated and the crystal structure determined by X-ray crystallography. The complex crystallizes in the orthorhombic space group Pccn, with Z=4, a=21.0105(9), b=11.0387(5), c=19.1389(8), V=4438.9(3) Å3, Mr=1090.19,R1=0.0327 and wR2=0.0876. The structure revealed a centrosymmetric tetrameric Nb(IV) complex, consisting of a pair of edge-sharing bi-octahedral Nb22-OC2H5)4Cl2(OC2H5)2(HOC2H5)2 units that are joined by two axial oxo ligands. The Nb-Nb distance of 2.7458(3) Å is consistent with a single metal-metal bond.  相似文献   

9.
A new polynuclear copper (II) complex, derived from the azido-bridging ligand and 2-aminopyrimidine, has been synthesized and its 3-D structure has been determined by X-ray diffraction methods at two different temperatures. The compound crystallizes in the triclinic system space group, with the central copper atom lying on an inversion centre. The crystal structure is built up by trinuclear units (each of them contains two double end-on azido bridges) linked through two azide ions in an end-to-end (EE) fashion, to yield the polymer chain [Cu3(ampym)21,1-N3)41,3-N3)2(dmf)2]n. Magnetic susceptibility measurement shows a ferromagnetic interaction above 30 K, whereas a weak anti-ferromagnetic interaction prevails in the range of 30-2 K.  相似文献   

10.
A new molecular loop composed of two quadruply bonded Mo2(DAniF)2 units (DAniF=N,N-di-p-anisylformamidinate) linked by two chiral allene-1,3-dicarboxylate anions has been prepared from the reaction of [cis-Mo2(DAniF)2(MeCN)4](BF4)2 with the bis(tetraethylammonium) salt of allene-1,3-dicarboxylic acid. This compound, [cis-Mo2(DAniF)2]2(O2C-CHCCH-CO2)2 (1), has been characterized by X-ray crystallography and by 1H NMR and UV-Vis spectroscopy. The molecule possesses a center of inversion and hence is meso. There is only weak electronic coupling between the two Mo2 4+ units as revealed by electrochemical measurements.  相似文献   

11.
Reaction of [WVIS4]2− with ethane-1,2-dithiol edtH2 in the presence of the sulfide scavenger Cd2+ yielded the dinuclear tungstate syn-[{(edt)WV(O/S)}2(μ-S)2]2− (1), with the terminal S/O disordered over the two tungsten sites in the ratio 0.8:02. In the presence of thiocyanate, phosphine and CuI, the anionic cuboidal clusters of composition [{(SCN)3WV}2{CuI(PPh3)}23-S)4]2− (2) and (3, diphos = 1,2-bis(o-diphenylphosphinophenyl)ethane), and possibly via an intermediate [{(SCN)3WVS}2(μ-S)2]4−. The crystal and molecular structures of [Et4N]21, [Et4N]22 · H2O and [Et4N]23 · H2O have been determined.  相似文献   

12.
The metalloligand [Pt2(μ-S)2(PPh3)4] reacts with Bi(S2CNEt2)3 or Bi(S2COEt)3 in methanol to produce the orange cationic adducts [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]+ and [Pt2(μ-S)2(PPh3)4Bi(S2COEt)2]+, respectively, isolated as their hexafluorophosphate salts. An X-ray structure determination on [Pt2(μ-S)2(PPh3)4Bi(S2CNEt2)2]PF6 reveals the presence of a six-coordinated bismuth centre with an approximately nido-pentagonal bipyramidal coordination geometry. Fragmentation pathways for both complexes have been probed using electrospray ionisation mass spectrometry; ions [Pt2(μ-S)2(PPh3)2Bi(S2CXEtn)2]+ (X = O, n = 1, X = N, n = 2) are formed by selective loss of two PPh3 ligands, and at higher cone voltages the species [(Ph3P)PtS2Bi]+ is observed. Ions formed by loss of CS2 are also observed for the xanthate but not the dithiocarbamate ions.  相似文献   

13.
A series of triphenylphosphine coordinated silver α,β-unsaturated carboxylates of type [Ag(O2CR)(PPh3)n: n = 1, R = CH3CHCH (2a), (CH3)2CCH (2b), CH3CH2CHCH (2c), CH3CH2CH2CHCH (2d), PhCHCH (2e), CH2CH (2f); n = 2, CH3CHCH (3a), (CH3)2CCH (3b), CH3CH2CHCH (3c), CH3CH2CH2CHCH (3d)] were prepared by reaction of relative silver carboxylates (1a-1f) with triphenylphosphine in chloroform. These complexes were obtained in high yields and characterized by elemental analysis, 1H NMR, 13C NMR, 31P NMR and IR spectroscopy. Thermal stability of the complexes has been determined by TG analysis. The molecular structure of [Ag((O2CCHC(CH3)2))(PPh3)2] (3b) shows that the senecioato ligand is chelated with silver atom and generate, a distorted tetrahedron.  相似文献   

14.
Reaction of Cu(NO3)2 · 3H2O, N,N,N′,N′-tetramethyl-ethylenediamine (L) and sodium dicyanamide (Nadca) in aqueous medium yields a complex the {[Cu2L2(μ-1,5-dca)2(dca)2]}n complex, 1. Single crystal X-ray analysis reveals that complex 1 has a 1D infinite chain structure in which copper(II) ions are bridged by single dicyanamide anions in an end-to-end fashion. The coordination environment around copper(II) is distorted square pyramidal. Two among the four coordination sites of the basal plane are occupied by the nitrogen atoms of the diamine and two remaining sites are occupied by the terminal nitrogen atom of a bridging and of a monodentate dca anions. The fifth coordination site (apical) is occupied by a nitrogen atom from a bridging dca anion of an adjacent CuL(dca)2 moiety, yielding the [Cu2L2(μ-1,5-dca)2(dca)2] dinuclear unit. Dimeric units are connected to each other by single μ-1,5-dicyanamido group to form infinite 1D chains which propagate parallel to the crystallographic c-axis. The variable temperature magnetic susceptibility measurements evidenced weakly antiferromagnetic interactions (J = −0.26 cm−1) in {[Cu2L2(μ-1,5-dca)2(dca)2]}n, 1.  相似文献   

15.
The reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with an equivalent of Bz2S3 at ambient temperature gave [CpCr(CO)2]2S (3) [L.Y. Goh, T.W. Hambley, G.B. Robertson, Organometallics 6 (1987) 1051], novel complexes of [CpCr(CO)2(SBz)]2 (4) and together with [CpCr(SBz)]2S (5) as main products. Thermolytic studies showed that 4 underwent complete decarbonylation to give [CpCr(SBz)]2S (5). Final thermal decomposition of 3 and 5 eventually yielded Cp4Cr4S4 (6) (Goh et al., 1987) after prolonged reaction at 100 °C. However, the reaction of [CpCr(CO)2]2 (CrCr) (2) with Bz2S3 was much slower at ambient temperature which required 72 h to complete eventually yielding 3 and 5. All the products have been characterized by elemental and spectral analyses. 4 has been structurally determined.  相似文献   

16.
Reaction of the metalloligand [Pt2(μ-S)2(PPh3)4] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt2(μ-S)2(PPh3)4] that contain NHC ligands, namely [Pt2(μ-S)2(PPh3)4AuL]+ (L = IPr, IMes) and [Pt2(μ-S)2(PPh3)4AgIMes]+. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt2(μ-S)2(PPh3)4] with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph3PAuCl, which undergoes double addition giving [Pt2(μ-SAuPPh3)2(PPh3)4]2+. The X-ray structure of [Pt2(μ-S)2(PPh3)4AuIPr]PF6 was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr+ moiety.  相似文献   

17.
《Inorganica chimica acta》2004,357(2):571-580
Treatment of the ligand N-(2-mercaptoethyl)-3,5-dimethylpyrazole with [Pd(CH3COO)2]3 and reaction of [PdCl(μ-med)]2 with pyridine (py) or triphenylphosphine (PPh3) in the presence of AgBF4 produced the following complexes: [Pd(CH3COO)(μ-med)]2, [Pd(μ-med)(py)]2(BF4)2 and [Pd(μ-med)(PPh3)]2(BF4)2. Similar reactions carried out with 2,2-bipyridine (bpy) or 1,3-bis(diphenylphosphino)propane (dppp) produced [Pd(μ-med)(bpy)]x(BF4)x (x=1 or 2) and [Pd(μ-med)(dppp)]x(BF4)x (x=1 or 2). Treatment of [Pd(μ-med)(bpy)]x(BF4)x with [PdCl2(CH3CN)2] produced [Pd3Cl2(μ-med)2(bpy)2](BF4)2. Treatment of [Pd(μ-med)(dppp)]x(BF4)x with [PdCl2(CH3CN)2] produced a mixture of [Pd(μ-Cl)(dppp)]2(BF4)2 and [Pd(μ-med)2(dppp)]2+. X-ray crystal structures of [Pd(μ-med)(PPh3)]2(BF4)2 · 2CH3CN and [Pd(μ-med)(bpy)]2(BF4)2 · 0.5CH3OH are presented.  相似文献   

18.
19.
The novel polynuclear [{Ru3O(CH3COO)6(py)2}2(BPEB)](PF6)2 species containing the linear bridging trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene ligand (BPEB) was synthesized and its structural characterization carried out by means of positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry, as well as by 1H NMR spectroscopy. The doubly charged cation [{Ru3O(CH3COO)6(py)2}2(BPEB)]2+ was detected in the ESI-MS mass spectrum as a multiple-component isotopomeric ionic cluster centered at m/z 974, which ion abundance and m/z distribution matched perfectly the isotopic pattern calculated for this multiple isotope Ru3-containing ion. The tandem mass spectrum of [{Ru3O(CH3COO)6(py)2}2(BPEB)]2+ provided a structural diagnostic dissociation behavior, on the basis of the characteristic charge splitting and sequential ligand loss steps. The cyclic voltammograms of the complex exhibited a quasi-reversible multistep redox behavior, displaying three waves at 1.14, 0.08, and −1.21 V ascribed to the [Ru3O]2+/1+/0/1− processes and two waves at −1.56 and −1.78 V ascribed to the BPEB0/1−/2− redox processes which are also observed in the free ligand, at −1.48 and 1.61 V, respectively. In spite of the conducting nature of the bridging ligand, the electrochemical and spectroelectrochemical results indicated a weak electronic coupling between the triangular cluster centers.  相似文献   

20.
1,25D3 is critical for the maintenance of normal reproduction since reduced fertility is observed in male rats on a vitamin D-deficient diet. Vitamin D-deficient male rats have incomplete spermatogenesis and degenerative testicular changes. In the present study we have examined the ionic involvement and intracellular messengers of the stimulatory effect of 1,25D3 on amino acid accumulation in immature rat testis. 1,25D3 stimulates amino acid accumulation from 10−12 to 10−6 M by increasing the slope to reach a maximum value at 10−10 M, as compared to the control group. No effect was observed at a lower dose (10−13 M). Time-course showed an increase on amino acid accumulation after 15, 30, and 60 min of incubation with 1,25D3 (10−10 M). 1,25D3 stimulated amino acid accumulation in 11-day-old rat testis but not in testis that were 20 days old. Cycloheximide totally blocked the 1,25D3 action on amino acid accumulation. Furthermore, a localized elevation of cAMP increased the stimulatory effect of 1,25D3 and the blockage of PKA nullified the action of the hormone. In addition, 1,25D3 action on amino acid accumulation was also mediated by ionic pathways, since verapamil and apamine diminished the hormone effect. The stimulatory effect of 1,25D3 on amino acid accumulation is age-dependent and specific to this steroidal hormone since testosterone was not able to change amino acid accumulation in both ages studied. This study provides evidence for a dual effect for 1,25D3, pointing to a genomic effect that can be triggered by PKA, as well as to a rapid response involving Ca2+/K+ channels on the plasma membrane.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号