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1.
《Inorganica chimica acta》1988,153(3):145-153
The blue complexes produced by reaction of cis-diamminediaquoplatinum(II) nitrate, [cis-Pt(NH3)2(H2O)2](NO3)2, with disodium 5′-uridine monophosphate, 5′-UMP(Na2), in H2O and D2O have been investigated by FT-IR spectroscopy. On the basis of the spectral changes observed in the CO stretching region during the reactions, chelation of the amidate N(3)··O(2) moiety to Pt(II) appears to be more likely than N(4)··O(4) chelation. The antisymmetric PO stretching mode of the PO32− group of 5′-UMP splits into a triplet on complex formation indicating that PO32− plays an important role in the structure of the platinum blue complexes. In addition, the sugar moiety of 5′-UMP apparently adopts a predominantly C(3′)-endo conformation in the solid blue complex. Finally, Raman microprobe spectroscopy of the solid provides some evidence for PtN(3) bond formation.  相似文献   

2.
Four complexes [Pd(L)(bipy)Cl]·4H2O (1), [Pd(L)(phen)Cl]·4H2O (2), [Pt(L)(bipy)Cl]·4H2O (3), and [Pt(L)(phen)Cl]·4H2O (4), where L = quinolinic acid, bipy = 2,2’-bipyridyl, and phen = 1,10-phenanthroline, have been synthesized and characterized using IR, 1H NMR, elemental analysis, and single-crystal X-ray diffractometry. The binding of the complexes to FS-DNA was investigated by electronic absorption titration and fluorescence spectroscopy. The results indicate that the complexes bind to FS-DNA in an intercalative mode and the intrinsic binding constants K of the title complexes with FS-DNA are about 3.5?×?104 M?1, 3.9?×?104 M?1, 6.1?×?104 M?1, and 1.4?×?105 M?1, respectively. Also, the four complexes bind to DNA with different binding affinities, in descending order: complex 4, complex 3, complex 2, complex 1. Gel electrophoresis assay demonstrated the ability of the Pt(II) complexes to cleave pBR322 plasmid DNA.  相似文献   

3.
The influences of water solvent on the structures and stabilities of the complex ion conformers formed by the coordination of alanine dipeptide (AD) and Na+ have been investigated using supramolecular and polarizable continuum solvation models at the level of B3LYP/6-311++G**, respectively; 12 monohydrated and 12 dihydrated structures of Na+–AD complex ion were obtained after full geometrical optimization. The results showed that H2O molecules easily bind with Na+ of Na+–AD complex ion, forming an ion-lone pair interaction with the Na–O bond length of 2.1–2.3 Å. Besides, H2O molecules also can form hydrogen bonds OW–HW···O(1), OW–HW···O(2), N(1)–H(1)···OW or N(2)–H(2)···OW with O or N groups of the Na+–AD backbone. The most stable gaseous bidentate conformer C7AB of Na+–AD is still the most stable one in the solvent of water. However, the structure of the most unstable gaseous conformer α′B of Na+–AD collapses under the attack of H2O molecules and changes into C7AB conformation. Computations with IEFPCM solvation model of self-consistent reaction field theory give that aqueous C5A is more stable than C7eqB and that the stabilization energies of water solvent on monodentate conformers of Na+–AD complex ion (about 272–294 kJ/mol) are more than those on bidentate ones (about 243 kJ/mol).  相似文献   

4.
The ternary complex [Cu(5′-IMP)(dpa)(H2O)]2 has been prepared and its structure analyzed by x-ray diffraction. It has a dimeric structure in which the 5′-IMP ligands coordinate solely through their phosphate groups. This geometry is in marked contrast to that of another Cu5′-IMP ternary complex, [Cu(5′-IMPH)(bipy)(H2O)2]+, which shows metal binding through the purine base rather than the phosphate group.  相似文献   

5.
The reaction of xanthosine-5′'-monophosphate disodium salt (5′-XMPNa2) with Pt(II), Cu(II) and Mg(II) ions produced compounds of the type cis- and trans-Pt(NH3)2(XMPNa2)nCl2·xH2O, where n = 1 or 2; Pt(XMPNa2)nCl2·xH2O, where n = 1-4, x = 1,4 & 6; Cu(XMP)·6H2O and Mg(XMP)·xH2O, where x = 9 or 4. In the complexes synthesized here at neutral pH values, the nucleotide binds through the N7-atom of the purine ring system, whereas for Cu(II) and Mg(II) compounds obtained at pH = 4 a direct metal-phosphate interaction as well as Nτ bonding is proposed.  相似文献   

6.
A novel ternary complex, Tb2L4·L′·(ClO4)6·8H2O, has been synthesized using bis(benzylsulfinyl)methane as the first ligand L and 2,2′‐dipyridyl as the second ligand L′. The ternary complex was characterized by element analysis, molar conductivity, coordination titration analysis, infrared, thermogravimetric‐differential scanning calorimetric and ultraviolet spectra. The results indicated that the composition of the complex was Tb2L4·L′·(ClO4)6·8H2O (L = C6H5CH2SOCH2SOCH2C6H5; L′ = Dipy). Fourier transform infrared results revealed that the perchlorate group was bonded with the Tb(III) ion by the oxygen atom, and the coordination was bidentate. The fluorescent spectra illustrated that the complex displayed characteristic fluorescence in the solid state. After the introduction of the second ligand, 2,2‐dipyridyl, the relative emission intensity and fluorescence lifetime of the ternary complex Tb2L4·L′·(ClO4)6·8H2O were enhanced compared to the binary complex TbL2.5(ClO4)3·3H2O. This indicated that the presence of both organic ligand bis(benzylsulfinyl)methane and the second ligand 2,2‐dipyridyl could sensitize the fluorescence intensity of Tb(III) ion, and introduction of the 2,2‐dipyridyl group resulted in an enhancement of the fluorescence of the Tb(III) ternary rare earth complex. The strongest characteristic fluorescence emission intensity of the ternary complex was 9.36 times that of the binary complex. The phosphorescence spectra and fluorescence lifetime of the complex were also measured. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

7.
Complexes of Co(II), Ni(lI), Cu(II), Zn(II) and Pt(II) with 1-formylisoquinoline thiosemicarbazone (1-iqtsc-H) were prepared and characterized by elemental analyses, conductance measurement and spectral studies. On the basis of these studies a distorted octahedral structure for [Co(1-iqtsc)2]·2H2O, a distorted trigonal-bipyramidal structure for [Ni- (1-iqtsc-H)Cl2], [Cu(1-iqtsc-H)Cl2] and [Zn(1-iqtsc- H)(OAc)2]·H2O and a square-planar structure for [Pt(1-iqtsc)Cl] are suggested. All these metal(II) complexes were screened for their antitumour activity in the P388 lymphocytic leukaemia test system in mice. Except for Pt(Il), the complexes were found to possess significant activity; the Ni(II) complex showed a T/C value of 161 at the optimum dosage.  相似文献   

8.
The acetylacetonates VO(acac)2, M(acac)3, where M = V, Mn or Fe and [M′(acac)2]n, where M′ = Co, Ni or Cu, have been reacted with pyridine-2,6-dicarboxylic acid (dipicH2) in acetone to afford the complexes VO(dipic)·2H2O, M(acac)(dipic)·xH2O [M = V, Mn or Fe and x = 1 or 0] and M2(dipic) (dipicH)2·yH2O [M = Co, Ni or Cu and y = 2 or 0]. The cobalt(II) and nickel(II) complexes are converted to polymeric [M(dipic)]n in ethanol and all three complexes formulated as M2(dipic)(dipicH)2 react with 2,2′2″-terpyridyl to yield M(dipic)(terpy)·3H2O. The vanadium(III) complex V(acac)(dipic) is oxidized to VO(dipic)·4H2O in aqueous solution via the vanadium(III) intermediate V(OH)(dipic)·2H2O. Tentative structural conclusions are drawn for certain of these new complexes based upon room temperature spectral and magnetic measurements. The characterization of these complexes has included selected studies of their X-ray photoelectron spectra.  相似文献   

9.
1‐phenyl‐3‐methyl‐4‐benzoyl‐5‐pyrazolone 4‐ethyl‐thiosemicarbazone (HL) and its copper(II), vanadium(V) and nickel(II) complexes: [Cu(L)(Cl)]·C2H5OH·( 1 ), [Cu(L)2]·H2O ( 2 ), [Cu(L)(Br)]·H2O·CH3OH ( 3 ), [Cu(L)(NO3)]·2C2H5OH ( 4 ), [VO2(L)]·2H2O ( 5 ), [Ni(L)2]·H2O ( 6 ), were synthesized and characterized. The ligand has been characterized by elemental analyses, IR, 1H NMR and 13C NMR spectroscopy. The tridentate nature of the ligand is evident from the IR spectra. The copper(II), vanadium(V) and nickel(II) complexes have been characterized by different physico‐chemical techniques such as molar conductivity, magnetic susceptibility measurements and electronic, infrared and electron paramagnetic resonance spectral studies. The structures of the ligand and its copper(II) ( 2 , 4 ), and vanadium(V) ( 5 ) complexes have been determined by single‐crystal X‐ray diffraction. The composition of the coordination polyhedron of the central atom in 2 , 4 and 5 is different. The tetrahedral coordination geometry of Cu was found in complex 2 while in complex 4 , it is square planar, in complex 5 the coordination polyhedron of the central ion is distorted square pyramid. The in vitro antibacterial activity of the complexes against Escherichia coli, Salmonella abony, Staphylococcus aureus, Bacillus cereus and the antifungal activity against Candida albicans strains was higher for the metal complexes than for free ligand. The effect of the free ligand and its metal complexes on the proliferation of HL‐60 cells was tested.  相似文献   

10.
The reaction of Cu(ClO4)2·6H2O with the Schiff base derived from 1,1′-(2,6-pyridyl)-bis-1,3-butanedione and 3-amino-1-propanol, (H4L2), yields the complex Cu(H4L2)(ClO4)2·H2O. The crystal structure of this complex is triclinic, R = 0.0521, 5602 reflections. The species is dimeric leading to a binuclear copper(II) complex in which the well- separated (8.93 Å intramolecular and 5.46 Å inter- molecular) copper(II) atoms are in distorted square pyramidal geometries.  相似文献   

11.
A novel ternary complex, TbL5L′(ClO4)3·3H2O, two binary complexes, TbL7(ClO4)3·3H2O and TbL′3.5(ClO4)3·4H2O has been synthesized (using diphenyl sulphoxide as the first ligand L, bipyridine as the second ligand L′). Their composition was analysed by element analysis, coordination titration, IR spectra and 1H‐NMR, and the fluorescence emission mechanism, fluorescence intensities and phosphorescence spectra were also investigated by comparison. It was shown that the ternary rare‐earth complex showed stronger fluorescence intensities than the binary rare‐earth complexes in such material. The strongest characteristic fluorescence emission intensity of the ternary system was 8.23 times, 3.58 times as strong as that of the binary systems TbL7(ClO4)3·3H2O and TbL′3.5 (ClO4)3·4H2O, respectively. By fluorescence analysis it was found that both diphenyl sulphoxide and bipyridine could sensitize the fluorescence intensities of rare‐earth ions. In particular, in the ternary rare‐earth complex, introduction of bipyridine was of benefit to the fluorescence properties of Tb(III). Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

12.
《Inorganica chimica acta》1986,115(2):153-161
In the reaction of the tetradentate ligand 3,3′-(1,4- butanediyldiamino) bis (3-methyl-2-butanone)-dioxime (BnAO) with nickel(II) and copper(II), the monomeric [Ni(BnAO-H)]I·H2O and a mixed monomer/dimer salt [Cu(BnAO-H)H2O]2[(Cu(BnAO-H))2](ClO4)4, respectively, are formed, and all complexes have an intramolecular hydrogen bond between cis oxime groups. The OHO bonds give the characteristic infrared absorptions as well as the downfield proton-NMR signal (Ni complex). [Ni(BnAO-H)]I·H2O crystallizes in space group P21/a with a=13.511(2), b=10.599(2), c=14.096(2) Å, β=97.52°, Z=4 and Dc=1.623 g/cm3. The structure was solved by Patterson and Fourier methods and refined by full-matrix least-squares techniques to a final R of 0.021 for 2124 reflections with I 2σ(I). The nickel(II) atom in the complex has slightly distorted square planar geometry with an intramolecular O···O contact of 2.417(7) Å. The copper(II) complex crystallizes in space group P21/c with a =13.425(2), b=21.446(3), c=14.349(4) Å, β= 104.4(5)°, Z=8 (monomers) and Dc=1.485 g/cm3. The final R value for this complex was 0.053 for 3033 reflections with I 2σ(I). This structure contains a monomeric [Cu(BnAO-H)H2O]+ ion and a dimeric [(Cu(BnAO-H))2]2+ ion, having intramolecular O···O hydrogen bonds of 2.421(5) and 2.531(5) Å, respectively. The copper(II) ions have square-pyramidal coordination with the axial positions occupied by an oxygen of the water of hydration in the monomer and by an oxime oxygen atom in the dimer. A center of symmetry relates the two halves of the dimer. The copper atom in each case is out of the plane of the four nitrogen atoms toward the axial site. The copper(II) complex is unusual in that the crystal contains both a monomer and a dimer.  相似文献   

13.
N-substituted ethylcarbamates form with thorium nitrate the complexes Th(NO3)4·3RHNC(O)OC2H5 (where R = CH3, C2H5, C6H5(CH3)CH) and with lanthanum nitrate the complexes La(NO3)3· 2RR′NC(O)OC2H5·3H2O (where R = CH3, C2H5, C6H5(CH3)CH; R′ = H and R = CH3, C6H5; R′ = C2H5 or R = R′ = CH3). In addition the anhydrous La(NO3)3·3(C2H5)2NC(O)OC2H5 has been isolated. From the IR spectra it is deduced that the carbamates coordinate the metal through the carbonyl oxygen atom and that the nitrato groups act as chelated ligands. 1H nmr spectral data of the complexes are reported and discussed.  相似文献   

14.
The preparation and molecular and crystal structure of the complex [(ethylenediamine)bis(7,9,-dimethylhypoxanthine)platinum(II)] hexafluorophosphate, [Pt(C2H8N2)(C7H8N4O)2] (PF6)2, are reported. The complex crystallizes in the monoclinic system, space group C2/c, with a = 12.334(2)Å, b = 10.256(2)Å, c = 22.339(3)Å, β = 101.31(1)°, V = 2771.0Å3, Z = 4, Dmeasd = 2.087(3) g cm?3, Dcalc = 2.094 g cm?3. Intensities for 3992 symmetry-averaged reflections were collected in the θ-2o scan mode on an automated diffractometer employing graphite-monochromatized MoKα radiation. The structure was solved by standard heavy-atom Patterson and Fourier methods. Full matrix least-squares refinement led to a final R value of 0.051. Both the ethylenediamine chelate and the PF6? anion are disordered. The primary coordination sphere about the Pt(II) center is approximately square planar with the bidentate ethylenediamine ligand and the N(1) atoms [Pt(II) ? N(1) = 2.020(5)Å] of two 7,9-dimethylhypoxanthine bases (related by a crystallographic twofold axis of symmetry) occupying the four coordination sites. The exocyclic O(6) carbonyl oxygen atoms of the two 7,9-dimethylhypoxanthine ligands participate in intracomplex hydrogen bonding with the amino groups of the ethylenediamine chelate [N(ethylenediamine) ? O(6) = 2.89( )Å]. The observed Pt ? O(6) intramolecular distances of 3.074(6)Å are similar to those found in other Pt(II) N(1)-bound 6-oxopurine complexes and in several Pt(II) N(3)-bound cytosine systems.  相似文献   

15.
A 1:1 complex of mercuric chloride with D-peniccillamine has been isolated and characterised as 2[(μ3-Cl){HgSC(CH3)2CH(NH3)COO}3]·3(μ2-Cl)·2(H3O)·(H2O·Cl)3. The compound crystallises in cubic space group P4132, with a = 18.679(5) Å and Z = 4. The structure, refined to RF = 0.086 for 443 observed Mo-Kα diffractometer data, features a triply bridging chloride ion linking three equivalent [HgSC(CH3)2CH(NH3)COO]+ units [Hg-Cl = 2.37(1) Å, Hg-Cl-Hg′ = 98.5(9)°]. The carboxylate groups of a pair of adjacent penicillamine ligands are strongly linked via a symmetrical O?H?O hydrogen bond of length 2.24(8) Å, and neighboring pyramidal trinuclear [μ3-Cl){HgSC(CH3)2CH(NH3)-COO}3]2+ moieties are further connected by symmetrical chloride bridges [Hg-Cl = 3.06(2) Å; HgClHg′' = 79.6(7)°] to form a three-dimensional network. The voids in the lattice are filled by hydronium ions and novel planar cyclic hydrogen-bonded (H2O·Cl?)3 rings of edge O-H?Cl = 2.46(4) Å.  相似文献   

16.
《Inorganica chimica acta》2006,359(8):2407-2416
The trimethyltin(IV) polymer [(Me3Sn)2(nip) · EtOH]n (1) of 5-nitroisophthalic acid (H2nip) and its three derivatives with mixed organic N-donor ligands 2,2′-bipy [(Me3Sn)2(nip) · 2H2O] · [(Me3Sn)2(nip) · H2O] · 2(2,2′-bipy) (2) 4,4′-bipy {[(Me3Sn)2(nip)]2(4,4′-bipy)}n (3) or phen [(Me3Sn)2(nip) · H2O] · (phen) (4) have been synthesized by the reaction of trimethyltin(IV) chloride and H2nip when sodium ethoxide was added in the presence of 2,2′-bipy 4,4′-bipy or phen. All complexes 14 were characterized by elemental, IR, 1H, 13C, and 119Sn NMR spectroscopy and X-ray crystallography analyses. Crystal, data collection and structure refinement parameters for complexes 1, 2, 3 and 4 are shown in Table 1, Table 2, respectively. The X-ray data showed the geometries of all the tin atoms in complexes 14 are trigonal bipyramidal. The X-ray analysis of 1 showed that the structure was a polymeric infinite chain with neighboring triorganotin centers being linked by dicarboxylate ligands and hydrogen bonds were found between adjacent chains. For 2, two different monomers were found, in one monomer, Me3Sn were coordinated to both carboxyl groups of the ligand and water molecules were coordinated to the two Sn(IV) centers. In the other monomer, water molecules were coordinated to only one Sn center. Co-crystallized2,2′-bipy was found in 2 and a 2D supermolecular structure was formed via O–H⋯O and O–H⋯N (N atoms derived from 2,2′-bipy) hydrogen bonds. In 3 however, a 2D polymeric block was formed due to the inversion center of the 4,4′-bipy. For 4, due to the O–H⋯O and O–H⋯N (N atoms derived from phen) hydrogen bonds and intermolecular Sn⋯O bonds, a 2D polymeric structure was formed.  相似文献   

17.
Taste effects of six newly synthesized ribonucleotide derivatives, i.e., disodium salts of 2-methyl-5′-inosinic acid · 6H2O, 2-ethyl-5′-inosinic acid · 1.5H2O, 2-N-methyl-5′-guanylic acid · 5.5H2O, 2-N-dimethyl-5′-guanylic acid · 2.5H2O, 2-methylthio-5′-inosinic acid · 6H2O and 2-ethylthio-5′-inosinic acid · 2H2O, were studied. Stimulus thresholds (detection thresholds) of these derivatives ranged from about 0.02 to 0.006 g/100ml. Flavor-enhancing activities of them were 2.3 to 8.0 times larger than that of disodium 5′-inosinate · 7.5H2O IMP) in the synergistic effect with monosodium glutamate. Furthermore, the quality of taste of all the derivatives was recognized to be the same kind to that of IMP.  相似文献   

18.
New complexes of the general compositions M(LH)X2 (M = Co, Zn; X = Cl, Br, I), Zn(LH)(NCS)2, Zn(LH)(NO3)2 ·H2O, Cu(LH)X2 (X = Cl, Br, ONO2), Ni(LH)Cl2·H2O, Co(LH)2X2 (X = NCS, ONO 2), Ni(LH)2X2 (X = Cl, Br, NCS, ONO2), Pt(LH)2Cl2 and MLCl·nH2O (M = Ni, Cu, Pd; n = 2, 3), where LH = N-(2-pyridyl)pyridine-2′-carboxamide, have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, X-ray powder patterns, thermal methods, magnetic susceptibilities and spectroscopic (IR, ligand field, 1H NMR) studies. Pseudotetrahedral, square planar, square pyramidal and distorted octahedral stereochemistries are tentatively assigned in the solid state. Most complexes appear to be monomeric, while polymeric structural types are attributed for Ni(LH)Cl2·H2O and CuLCl·2H2O. The neutral amide group of LH is coordinated to Co(II), Ni(II), Cu(II) and Zn(II) through oxygen, while N-coordination is observed for PdLCl·2H2O. The amide group of L is bound to different Cu(II) atoms in CuLCl·2H2O through both its nitrogen and oxygen. The rare O-coordination of the deprotonated amide bound is proposed for NiLCl· 3H2O. The N(1) atom is not involved in coordination except in the complexes Ni(LH)Cl2·H2O, NiLCl· 3H2O and CuLCl·2H2O, where both pyridine residues are coordinated. The variation in structural types observed is believed to be a consequence of the stereochemical adaptability of the ligand to the electronic demands of the metal ions.  相似文献   

19.
The X-ray photoelectron spectra for (NH4)3 [Rh(S5)3]·2H2O and (NH4)2[PtS17]·2H2O are consistent with those previously reported for (NH4)2 [Pt(S5)3]·2H2O, where different electron binding energies were observed for the structurally distinct sulfur atoms in the polysulfido ligands. The 4f binding energies for the platinum polysulfides are lower than those for platinum(IV) bonded to elements other than sulfur, and the 3d binding energies for the rhodium complex are lower than most values for rhodium(III) bonded to oxygen or nitrogen.  相似文献   

20.
2,2′-Diaminobiphenyl-R,R-trans-1,2-diaminocyclohexaneplatinum(II) Chloride Trihydrate, (R,R-chxn)(dabp)Pt]Cl2·3H2O, crystallizes in the space group p212121 (D24, No. 19) with a = 6.219(4) Å, b = 17.633(2) Å, c = 21.523(3) Å, V = 2,360.4(8) Å3, ?calcd = 1.739 g cm?3, ?measd = 1.74 g cm?3, and Z = 4. Diffraction data were collected with a Picker FACS-1 four-circle diffractometer. The structure was solved by the heavy atom method and refined by least-square calculations to residuals R = 0.0586 and weighted R = 0.0668. The 2,2′-diaminobiphenyl ligand exhibits complete stereospecificity in its coordination to platinum(II) ion with λ chiral conformation.  相似文献   

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