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1.
The predominant complex formed by the reaction of cis-(NH3)2PtCl2 and guanylyl(3′-5′)cytidine has been isolated. The molar ratio of the binding of cis-(NH3)2PtCl2 to guanylyl(3′-5′)-cytidine is 1:2. The values of proton dissociation constant due to guanine and cytosine bases provide useful information for determining the binding site of the isolated complex. In addition, nmr and ir spectral data were used to determine the binding site. cis-(NH3)2PtCl2 coordinates to guanylyl(3′-5′)cytidine through N(7) position of the guanine base, but cytosine base does not participate in the binding to cis-(NH3)2Pt2+. Interbase crosslink has not been detected. The binding specificity of cis-(NH3)2PtCl2 to guanine base is discussed.  相似文献   

2.
Reaction of benzisothiazolinone (Bit), a well-known biocide, with the Pd(II) and Pt(II) am(m)ine precursors cis-[Pd(en)(H2O)2](NO3)2 and cis-[Pt(NH3)2(H2O)2](NO3)2 yielded cis-Pd(en)(Bit−1H)2 and cis-Pt(NH3)2(Bit−1H)2, respectively. Bit is bound to the metal centres in both cases through the deprotonated isothiazolinone N. The crystal structures of a Bit/BitO co-crystal and cis-Pd(en)(Bit−1H)2·H2O are also described.  相似文献   

3.
An eight-step synthesis is described which gives an overall yield of ~30% methyl cis-9,cis-12-octadecadienoate-16,16,17,17-d4. The preparation utilizes easily obtainable starting materials. Tris(triphenylphosphine)chlororhodium (I) catalyst is used for incorporation of the deuterium isotopes. The double bond in the 9 position is created by the Wittig coupling of 1-non-3-enyl-d4-triphenylphosphonium bromide to methyl 8-formyloctanoate. Various methods for preparation of the intermediate and final products are discussed. Partial argentation resin chromatography was used to remove the ~9% trans/cis, cis/trans, and trans/trans isomers also produced. Analysis of the final product by mass spectrometry (MS) indicated 96%-d4.  相似文献   

4.
The reaction of cis-[ReO2I(PPh3)2] with 3-methyl-2-aminophenol (H2map) in ethanol led to the formation of trans-[Re(map)(Hmap)I(PPh3)2]I. The X-ray crystal structure shows that the ligand map is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hmap is coordinated via the neutral amino nitrogen and the singly deprotonated phenolate oxygen, which is coordinated trans to the imido nitrogen. In benzene equimolar quantities of cis-[ReO2I(PPh3)2] and 4-methyl-2-aminophenol (H2amp) produced the five-coordinate cis-[ReO2(Hamp)(PPh3)]. A twofold molar excess of 2-aminophenol (H2ap) yielded the six-coordinate [ReO(Hap)(ap)(PPh3)]. The chelate ap is coordinated through the deprotonated phenolate oxygen and the singly deprotonated amino nitrogen (amide).  相似文献   

5.
Cinerone [2-(2′-cis-butenyl)-3-methyl-2-cyclopenten-1-one] is hydroxylated to cinerolone [2-(2′-cis-butenyl)-3-methyl-4-hydroxy-2-cyclopenten-1-one] by a number of streptomycetes, bacteria, and fungi. Aspergillus niger ATCC 9,142 and Streptomyces aureofaciens ATCC 10,762 were found to be the most effective hydroxylators. The optical activity of the product was found to range from [α]D25 0° to -8.6°, depending on the organism and conditions of culture. Two additional hydroxylated products of cinerone have been isolated and identified as 2-n-butyl-4-hydroxy-3-methyl-2-cyclopenten-1-one and 2-(2′-cis-butenyl-4′-hydroxy)-3-methyl-2-cyclopenten-1-one, respectively.  相似文献   

6.
The structure and reactivity of the complex [Ru(2,3-Medpp)2Cl2](PF6)2 (2,3-Medpp+=2-[2-(1-methylpyridiniumyl)]-3-(2-pyridyl)pyrazine) was investigated by X-ray diffraction (XRD), 1H NMR, redox, and UV-Vis absorption measurements. X-ray analysis shows that crystals obtained from an acetonitrile-toluene solution contain the trans-Cl2, trans-pyrazine isomeric form, while 1H NMR and redox measurements on the main product of the synthetic workup indicate the presence of the trans-Cl2, cis-pyrazine isomer. In the dark at 70 °C, the complex [Ru(2,3-Medpp)2Cl2]2+ reacts slowly in acetonitrile isomerizing to the cis-[Ru(2,3-Medpp)2(CH3CN)Cl]3+ species. Under ambient light in the presence of excess AgNO3 the cis-[Ru(2,3-Medpp)2(CH3CN)2]4+ species is obtained.  相似文献   

7.
Self complementary deoxyribooctanucleotides, [5′-d(GpGpTpCpGpApCpC)-3′]2 and [5’-d(CpGpGp- ApTpCpCpG)-3’]2, were allowed to react with cis- PtCl2(NH3)2, and the reaction mixture was treated with exonuclease (snake venom phosphodiesterase and/or calf spleen phosphodiesterase). Semi-quantitative analysis by HPLC showed that the adjoining guanine bases have a specific binding affinity to cis-PtCl2(NH3)2.  相似文献   

8.
The seasonal variations in the amounts of C6-volatile components cis-3-hexenal trans-2-hexenal n-hexanal) and their precursors (linoleic and linolenic acid) in homogenates of Thea sinensis leaves were quantitatively analyzed throughout the year. Formation of trans-2-hexenal began in the middle of April and reached a maximum during July. Towards autumn the aldehyde gradually decreased and, in winter (December to March), was virtually absent. The levels of cis-3-hexenol remained constant during May–December. cis-3-Hexenal showed a similar variation pattern to that of trans-2-hexenal. The major fatty acids in the leaves were palmitic, palmitoleic, oleic, linoleic and linolenic acid, and occurred in non-ionic lipids and phospholipid fractions. The amounts of linoleic and linolenic acid did not show any marked variation except for a big peak in October.  相似文献   

9.
The crystal and molecular structure of Δ- cis-α- ethylenebis-S-prolinato(1,2-diaminoethane)cobalt(III) perchlorate dihydrate, Δ-cis-α-[Co(SS-EBP)(en)] ClO4· 2H2O, was determined from three-dimensional X-ray diffractometer data. The complex crystallizes in the orthorhombic system, space group P212121 with a = 7.879(4) Å, b = 13.738(9) Å, c = 19.445(2) Å, V = 2104(2) Å3. With Z = 4, the observed and calculated densities are 1.60(2) and 1.605 g cm?3, respectively. The structure was refined by the block- diagonal least-squares technique to a final R = 0.0560 for 1604 observed reflections. The geometry about the cobalt atom is roughly octahedral with the tetradentate SS-EBP (= ethylenebis-S-prolinate ion), assuming cis-α configuration in which the complex possesses two out-of-plane amino acidate (R) rings and the backbone ethylenediamine (E) ring. The E ring conformation is δ. On the other hand, the R rings have λ conformation as well as the en ring. Δ-RNRN?E  λR1  λR2)(λen)-cis-α-[Co(SS-EBP)(en)]+ is one of two possible isomers of this compound which have been isolated and whose absolute configurations have been tentatively assigned by spectroscopy. The crystal and molecular structure determination confirms these assignments.  相似文献   

10.
Because of its highly unstable nature, TXA2, produced by platelet metabolism of arachidonic acid, does not lend itself to use as a receptor probe for its own receptor. As such, the stable TXA2/PGH2 antagonist, trans-13-azaprostanoic acid (trans-13-APA, 12b), was prepared as the [17,18 3H] derivative ([3H] trans-13-APA, 12c) to study this receptor and to better evaluate the mechanism of action of these azaprostanoids. Tritiated trans-13-APA, 12c, was prepared in nearly theoretical specific activity (57 Ci/mmole) from (17z)-trans-13-azaprost-17-enoic acid (11b) by catalytic tritiation. The unsaturated 11b was prepared by condensation of cis-7-amino-3-heptene (8) with 2-(6-carboxyhexyl) cyclopentanone (9), NaBH4 reduction, chromatography, and hydrolysis of the trans isomer so isolated. The olefins 11a and b were also of biochemical interest because of the unsaturation in the lower side chain. The presence of similar unsaturation in PGH3 (4) and TXA3 (3) renders these prostaglandins inactive as proaggregatory agents. Evaluation of the antiaggregatory activity of 11a and b indicated it to be about the same potency in inhibiting human platelet aggregation as the parent cis and trans-13-APAs, suggesting that introduction of a double bond at the 17 position in platelet prostaglandin antagonists is unlikely to result in enhanced antiplatelet activity.  相似文献   

11.
Complexes of the types cis- and trans-Pt(amine)2I2 were studied by spectroscopic methods, especially by multinuclear NMR spectroscopy. In 195Pt NMR, the cis diiodo compounds with primary amines were observed between −3342 and −3357 ppm in acetone, while the trans compounds were found between −3336 and −3372 ppm. For the secondary amines, the chemical shifts were observed at lower fields. In 1H NMR, the trans complexes were observed at higher fields than the cis compounds, while in 13C NMR, the reverse was observed. The 2J(195Pt-1H) and 3J(195Pt-1H) coupling constants are larger for the cis compounds (ave. 67 and 45 Hz, respectively) than for the trans isomers (ave. 59 and 38 Hz). In 13C NMR, the values of 2J(195Pt-13C) and 3J(195Pt-13C) were also found to be larger for the cis complexes (ave. 17 and 39 Hz versus 11 and 28 Hz). There seems to be a slight dependence of the pKa values of the protonated amines or the proton affinity in the gas phase with the δ(Pt) chemical shifts. The crystal structures of eight diiodo complexes were determined. These compounds are cis-Pt(CH3NH2)2I2, cis-Pt(n-C4H9NH2)2I2, cis-Pt(Et2NH)2I2, trans-Pt(n-C3H7NH2)2I2, trans-Pt(iso-C3H7NH2)2I2, trans-Pt(n-C4H9NH2)2I2, trans-Pt(t-C4H9NH2)2I2 and trans-Pt(Me2NH)2I2. The Pt-N bond distances located in trans position to the iodo ligands were compared to those located in trans position to the amines. The Pt-N bond in cis-Pt(Et2NH)2I2 are much longer than the others, probably caused by the steric hindrance of the two very bulky ligands located in cis positions.  相似文献   

12.
A series of cis and trans tetradentate copper macrocyclic complexes, of ring size 14-16, that employ amine and thioether donor groups are reported. Apart from 5,6,15,16-bisbenzo-8,13-diaza-1,4-dithia-cyclohexadecane copper(I) (cis-[Cu(H4NbuSen)]+) all of the complexes are obtained in the copper(II) form. Crystallographic analysis shows that the copper(II) complexes all adopt a distorted planar geometry around the copper. In contrast, cis-[Cu(H4NbuSen)]+ is found to adopt a distorted tetrahedral geometry. The complexes were subjected to electrochemical analysis in water and acetonitrile. The effect of the solvent, positions of the donor atoms (cis/trans) on E1/2 is discussed as is the comparison of the electrochemical behaviour of these complexes with their parent Schiff base macrocycles.  相似文献   

13.
Complexes of the types cis- and trans-Pt(amine)2(NO3)2 with amines containing a phenyl group were synthesized and studied mainly by IR and multinuclear magnetic resonance spectroscopies. The cis complexes could be synthesized pure only with the amines of the type Ph-R-NH2 (R = alkyl), while pure trans compounds were synthesized with all the studied amines. In 195Pt NMR spectroscopy, the dinitrato complexes of the amines Ph-R-NH2 were observed around −1700 ppm for the cis isomers and at about −1580 for the trans complexes. For the other amines, where a phenyl ring is directly attached to the amino group, the signals were observed at lower fields, −1528 ppm for cis-Pt(PhNH2)(NO3)2 and around −1450 ppm for all the trans isomers. There is a linear relationship between the δ(Pt) of the Pt(amine)2(NO3)2 complexes and the pKa of the protonated amines. The coupling constants 2J(195Pt-1HN) are larger in the cis compounds (ave. 76 Hz) than in the trans isomers (ave. 63 Hz). The complexes cis-Pt(amine)2(R(COO)2) with bidentate dicarboxylato ligands were also synthesized and characterized mainly by IR spectroscopy. The compounds apparently decompose in DMF and are too insoluble in other solvents for solution studies.  相似文献   

14.
Reaction of tetrathiafulvalene carboxylic acid (TTFCO2H) with paddlewheel dirhodium complex Rh2(ButCO2)4 yielded TTFCO2-bridged complexes Rh2(ButCO2)3(TTFCO2) (1) and cis- and trans-Rh2(ButCO2)2(TTFCO2)2 (cis- and trans-2). Their triethylamine adducts [1(NEt3)2] and cis-[2(NEt3)2] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt3)2] is not completely separated from a mixture of cis- and trans-[2(NEt3)2], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO2 moiety and the last one is the oxidation of the Rh2 core. The oxidation of cis-2 is observed as a two-step process with very similar E1/2 values to those of the first two processes for 1. Both 1+ and cis-22+ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and aH = 0.135 mT for two equivalent H atoms and aH = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.  相似文献   

15.
Complexes of the types cis- and trans-Pt(amine)2I2 containing cyclic amines were synthesized and studied mainly by IR and multinuclear NMR spectroscopies. The compounds were converted to cis- and trans-Pt(amine)2(NO3)2, which were also investigated. The hydrolysis and the aquation reactions of the latter compounds were then studied in D2O in different conditions of pH. In acidic medium, the aqueous product is [Pt(amine)2(D2O)2]2+ and for a few amines, [Pt(amine)2(D2O)(NO3)]+ was detected. In basic pH, the main product is Pt(amine)2(OD)2 and Pt(amine)2(OD)(NO3) was detected for several compounds. In neutral pH, the cis isomers form between two and four species in fresh solutions. The most shielded species in 195Pt NMR is the monoaqua-monohydroxo complex cis-[Pt(amine)2(D2O)(OD)]+ and the less shielded compound is the dihydroxo-bridged dimer [Pt(amine)2(μ-OD)2Pt(amine)2]2+, which were observed for all the compounds. For a few amines, the monohydroxo-bridged dimer [Pt(D2O)(amine)2(μ-OD)Pt(OD)(amine)2]2+ was detected and for cyclohexylamine, a fourth signal was assigned to a cyclic hydroxo-bridged trimer [(Pt(amine)2(μ-OD))3]3+. 195Pt NMR spectroscopy has shown that the concentration of the monomer decreases with time, while the concentration of the dimers increases. Only one product was observed for the trans isomers in neutral pH. The signal was assigned to the monoaqua-monohydroxo species trans-[Pt(amine)2(D2O)(OD)]+. The 13C and 1H NMR spectra of most of the complexes were measured. All the coupling constants 2,3J(195Pt-1H) and 2,3J(195Pt-13C) are larger in the cis compounds than in the trans isomers.  相似文献   

16.
We report here the synthesis, characterization and kinetic studies of cis-[RuCl2(cyclen)]+ in aqueous solution, where cyclen is the macrocyclic ligand 1,4,7,10-tetraazacyclododecane. The complex releases one Cl producing cis-[RuCl(OH)(cyclen)]+ in aqueous solution at pH 4.60. The product of this reaction was characterized by Ultraviolet-Visible (UV-Vis) spectrum in comparison to the synthesized cis-[RuCl(OH)(cyclen)](BF4)·2H2O. The electrochemical data showed that Epc of the Ru(III/II) peak increases as the macrocycle ring size decreases and also when the trans conformation is changed to cis. The chloride affinity of Ru(III) depends on the macrocycle ring size since cis-[RuCl2(cyclam)]+ (cyclam=1,4,8,11-tetraazacyclotetradecane) does not release chloride for at least 12 h. The overall effect between cyclam and cyclen reflects the fact that the electron involved in the reduction enters a nonbonding π-d orbital and its energy is affected by the macrocyclic ligand.  相似文献   

17.
Octaprenyl diphosphate synthase (OPPs) and undecaprenyl diphosphate synthases (UPPs) catalyze consecutive condensation reactions of farnesyl diphosphate (FPP) with 5 and 8 isopentenyl diphosphate (IPP) to generate C40 and C55 products with trans- and cis-double bonds, respectively. In this study, we used IPP analogue, 3-bromo-3-butenyl diphosphate (Br-IPP), in conjunction with radiolabeled FPP, to probe the reaction mechanisms of the two prenyltransferases. Using this alternative substrate with electron-withdrawing bromo group at the C3 position to slow down the condensation step, trapping of farnesol in the OPPs reaction from radiolabeled FPP under basic condition was observed, consistent with a sequential mechanism. In contrast, UPPs reaction yielded no farnesyl carbocation intermediate under the same condition with radiolabeled FPP and Br-IPP, indicating a concerted mechanism. Our data demonstrate the different reaction mechanisms for cis- and tran-prenyltransferases although they share the same substrates.  相似文献   

18.
The reaction products of adenosine with [Pt(NH3)3Cl]Cl or cis-Pt(NH3)2Cl2 have been studied using high performance liquid chromatography and uv spectroscopy. The reaction of [Pt(NH3)3Cl]Cl with adenosine (pH = 7.0, Pt/base = 0.5) gives four products. Two of them, mononuclear complexes in which platinum is bound to adenosine through N(7) or N(1), comprise more than 90% of all the products. The N(1) and N(7) sites on adenosine indicate almost equal binding affinity for [Pt(NH3)3Cl]Cl. The reaction of cis-Pt(NH3)2Cl2 with adenosine has been studied in the presence of a large excess of adenosine (Pt/base ? 0.05). The reaction gives four products. One is the monomeric 2:1 complex with cis-Pt(NH3)22+ bound to two adenosine molecules through the N(7) site and the N(1) site, and another is the monomeric 2:1 complex with cis-Pt(NH3)22+ bound to two adenosine molecules through the N(7) sites. cis-Pt(NH3)2Cl2 is stronger affinity to the N(7) site than of adenosine to the N(1) site.  相似文献   

19.
The synthesis and characterisation of cis- and trans-[Co(tmen)2(NCCH3)2](ClO4)3 are described. Solvolysis rates have been measured by both 1H NMR spectroscopy and UV-Vis spectrophotometry in dimethyl sulfoxide at 298.2 K. The cis isomer undergoes solvolysis by consecutive first-order reactions, k1=5.61 × 10−4 and k2=5.35 × 10−4 s−1, each with steric retention. The measured solvolysis rate (single step reaction) for the trans isomer is k=1.54 × 10−5 s−1. The solvent exchange rates have been measured by 1H NMR spectroscopy in CD3CN at 298.2 K: kex(cis)=kct + kcc=2.0 × 10−5 and kex(trans)=ktc + ktt=4.56 × 10−6 s−1. From these data, the measured cis-trans isomerisation rate (1.71 × 10−6 s−1) and equilibrium position in CH3CN (17% trans), the steric course for substitution in the exchange processes has been determined: trans reactant - 69% trans product; cis reactant - 99% cis product. Aquation rates for cis- and trans-[Co(tmen)2(NCCH3)2](ClO4)3 have also been determined spectrophotometrically and by NMR; kcis=1.3 × 10−4 and ktrans=2.7 × 10−5 s−1. In both cases the steric course for the primary aquation step is indeterminate because the subsequent steps are faster. Where data are available, the [Co(tmen)2X2]n+ complexes are found to be consistently much more reactive than their [Co(en)2X2]n+ analogues.  相似文献   

20.
Novel ionic mixed-ligands complexes of the types cis- and trans-[Pt(amine)2(pm)2](NO3)2 (where pm = pyrimidine) were synthesized and studied in the solid state by IR spectroscopy and in aqueous solution by multinuclear (195Pt, 1H and 13C) magnetic resonance spectroscopy. The results of the solution NMR characterization have shown that the isolated compounds are pure. In 195Pt NMR, the cis RNH2 complexes were observed at slightly lower fields (ave. −2441 ppm) than the equivalent trans analogues (ave. −2448 ppm). For Me2NH, the difference between the two isomers is larger (29 ppm). The complexes are observed at lower fields (difference of 100 ppm) than the corresponding [Pt(amine)4]2+ complexes, which might indicate the presence of π-backdonation in the Pt-pm bond. In 1H NMR, the coupling constants 3J(195Pt-1Hamine) are larger in the cis compounds (38-48 Hz) than in the trans analogues (30-36 Hz). The 3J(195Pt-1Hpm) values are also larger for the cis isomers. In 13C NMR spectroscopy, the coupling constants 3J(195Pt-13Camine) are 36 Hz (ave.) for the cis complexes and 26 Hz (ave.) for the trans isomers, while the 2J(195Pt-13Camine) are 18 Hz (cis) and 14 Hz (trans), respectively. The 3J(195Pt-13C5(pm)) values are 36 Hz (cis) and 28 Hz (trans). A few 2J(195Pt-13Cpm) couplings were observed (7-10 Hz).  相似文献   

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