A comparison of six density functional theory (DFT) methods and six basis sets for predicting the molecular structures and vibration spectra of cisplatin is reported. The theoretical results are discussed and compared with the experimental data. It is remarkable that LSDA/SDD level is clearly superior to all the remaining density functional methods (including mPW1PW) in predicting the structures of cisplatin. Mean deviation between the calculated harmonic and observed fundamental vibration frequencies for each method is also calculated. The results indicate that PBE1PBE/SDD is the best method to predict all frequencies on average for cisplatin molecule in DFT methods. 相似文献
Triamines of platinum(II) (Pt(NH3)2LCl]Cl with a cis-structure (L represents cytosine, cytidine, isocytosine, theobromine, theophylline) and cis- and trans-isomers with theophylline and inosine were synthesized. The coordination formulas were demonstrated by methods of conductometry and long-wave spectroscopy. The coordination of pyrimidines through the N(3) atoms and purines through the N(7) atoms was established by PMR methods. An intensification of the acidic properties of the NH group of the ligands upon coordination with platinum was demonstrated. Cis-triamines have an antitumor effect on solid tumors and leukemias, which permits them to be assigned to a new class of water-soluble cationic monofunctional antitumor complexes of platinum(II).Leningrad Chemicopharmacological Institute. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 3, pp. 354–361, May–June, 1991. Original article submitted March 11, 1991. 相似文献
A comprehensive calculations were carried out to get a deep insight into the ground- and excited-state electronic structures and the spectroscopic properties for a series of [Pt(4-X–trpy)CCC6H4R]+ complexes (trpy = 2,2′,6′,2″-terpyridine; X = H, R = NO2 (1), Cl (2), C6H5 (3) and CH3 (4); R = Cl, X = CH3 (5) and C6H5 (6)). MP2 (second-order Møller–Plesset perturbation) and CIS (single-excitation configuration interaction) methods were employed to optimize the structures of 1–6 in the ground and excited states, respectively. The investigation showed that substituted phenylacetylide and trpy ligands only give rise to a small variation in geometrical structures but lead to a sizable difference in the electronic structures for 1–6 in the ground and excited states. The introduction of electron-rich groups into the phenylacetylide and/or terpyridyl ligands produces two different low-lying absorptions for 1 and 2–6, i.e., Pt(5d) → π*(trpy) metal-to-ligand charge transfer (MLCT) mixed with π → π*(CCPh) intraligand charge transfer (ILCT) for 1 and Pt(5d)/π(CCPh) → π*(trpy) charge transfer (MLCT and LLCT) for 2–6. Remarkable electronic resonance on the whole Pt–CCPh–NO2 moiety for 1 may be responsible for the difference. Solvatochromism calculation revealed that only LLCT/MLCT transitions showed the solvent dependence, consistent with the experimental observations. 相似文献
Organoplatinum antitumor agents are very effective, broad-spectrum drugs used for the treatment of a variety of cancerous
conditions. The two most prominent of these, Cisplatin [cis-diamminodichloroplatinum(II)] and Carboplatin [diammino(1,1-cyclobutanedicarboxylato)platinum(II)], are large scale commercial
successes. The third, Oxaliplatin [((trans-1,2-diamminocyclohexane)oxalato)platinum(II)], is now commercially available. The administration of all these drugs is accompanied
by severe side effects. For Cisplatin, the most debilitating of these is kidney damage and extreme nausea. Several approaches
to generate drug-release formulations that might mitigate toxic side effects have been explored. Now, platinum(IV) compounds
which are more inert than platinum(II) compounds, and consequently less toxic, but which may be reduced to platinum(II) species
within the cell are being evaluated for effectiveness in the treatment of cancer. The thermal stability of several precursors
to compounds of this kind has been examined by thermogravimetry. In general, these materials lose ligands sequentially to
generate a residue of platinum. This behavior may be generally useful for the characterization of such materials. 相似文献
The crystal and molecular structures of the title compounds, [PtCl3(C3H8N)] (I), [PtCl3(C4H10N)] (II), and [PtCl3(C6H14N)] (III) have been determined by single-crystal X-ray methods. I crystallizes in the orthorombic system (Pbca) with a 10.444(3), b 8.782(2), c 17.036(5)Å, Z 8; II is monoclinic (P21/n) with a 7.953(5), b 11.254(6), c 10.722(6)Å, β 111.07(4)°, Z 4; III is orthorombic (P212121) with a 17.080(6), b 6.768(2), c 9.541(4)Å, Z 4. Full-matrix least-squares refinements have given final R-factors of 0.051 (1077 reflections for I), 0.043 (1325 reflections for II) and 0.041 (1123 reflections for III). The reflections were collected by counter methods and only those having I τ 3σ(I) were used in the analyses.In all three complexes platinum is four-coordinate, having as ligands the three chlorine atoms and the double bond of the(n=1, 2 or 4) cationic species. The structures are discussed, and compared with that of the analogous complex containing the pent-4-enylammonium cation,. 相似文献
Reactions of [Pt2(μ-Cl)2(C∩P)2] (C∩P = CH2C(Me2)PBut2-C,P) with various anionic ligands differing in ligand bite and denticity have been investigated and the resulting products have been characterized by elemental analyses and NMR (1H, 13C, 31P, 195Pt) spectroscopy. Stereochemistry of the complexes has been deduced by NMR spectroscopy. Structures of [Pt2(μ-SPh)2(C∩P)2], [Pt2(μ-pz)2(C∩P)2], [PtCl(Spy)(PBut3)], [Pt2(μ-SCOPh)2(C∩P)2] and [Pt{S2P(OPri)2}(C∩P)] have been established by single crystal X-ray diffraction analyses. The complex [Pt2(μ-SPh)2(C∩P)2] adopts a sym cis configuration while other binuclear complexes exist in a sym trans configuration. The molecular structure of [Pt{S2P(OPri)2}(C∩P)] revealed that complex comprises of two four-membered chelate rings but in solution a dimeric structure based on 195Pt NMR data has been suggested. 相似文献
The new complexes [Pd(dmba)( N10-9AA)(PPh 3)]ClO 4 ( 1), [Pt(dmba)( N9-9AA)(PPh 3)]ClO 4 ( 2), [Pd(dmba)( N10-9AA)Cl] ( 3), and [Pd(C 6F 5)( N10-9AA)(PPh 3)Cl] ( 4) (9-AA = 9-aminoacridine; dmba = N,C-chelating 2-(dimethylaminomethyl)phenyl) have been prepared. The crystal structures have been established by X-ray diffraction. In complex 2, an anagostic C-H...Pt interaction is observed. All complexes are luminescent in the solid state at room temperature, showing important differences between the palladium and platinum complexes. Complex 2 shows two structured emission bands at high and low energies in the solid state, and the lifetimes are in agreement with excited states of triplet parentage. Density functional theory and time-dependent density functional theory calculations for complex 2 have been done. Values of IC 50 were also calculated for the new complexes 1- 4 against the tumor cell line HL-60. All of the new complexes were more active than cisplatin (up to 30-fold in some cases). The DNA adduct formation of the new complexes synthesized was followed by circular dichroism and electrophoretic mobility. Atomic force microscopy images of the modifications caused by the complexes on plasmid DNA pB R322 were also obtained. 相似文献
A series of palladium(II) and platinum(II) complexes possessing pentafluorophenyl ligands of the general formula [M(L-L)(C6F5)Cl][space](M = Pd 3; L-L=tmeda (N,N,N',N',-tetramethylethylenediamine) a; 1,2-bis(2,6-dimethylphenylimino)ethane) b; dmpe (1,2-bis(dimethylphosphino)ethane) c; dcpe (1,2-bis(dicyclohexylphosphino)ethane) d; Pt ; L-L=tmeda a; 1,2-bis[3,5-bis(trifluoromethyl)phenylimino]-1,2-dimethylethane b; dmpe c; dcpe d) were readily synthesized from the dimer [M(C6F5)(tht)(mu-Cl)2] (M=Pd 1b, Pt 2b; tht=tetrahydrothiophene) and the corresponding bidentate ligand. In the case of palladium, the corresponding iodo analogues (6a-c) were readily synthesized in a one-pot reaction from [Pd2(dba)3], iodopentafluorobenzene, and the appropriate ligand. The platinum complexes 4c-d were then converted to the water complexes [Pt(L-L)(C6F5)(OH2)]OTf (L-L =dmpe 7a; dcpe 7b)via reaction with AgOTf in the presence of water. Attempts to convert the palladium complexes 3c-d to the corresponding water complexes resulted in the disproportionation of the intermediate water complex to form [Pd(L-L)(C6F5)2] (L-L=dmpe 8) or [Pd(L-L)2][OTf]2(L-L=dcpe 9). Upon standing in solution for prolonged periods, complex 7a undergoes an identical disproportionation reaction to the Pd analogues to form [Pt(L-L)(C6F5)2] (L-L=dmpe 10). Complexes 4c and 4d were converted to the corresponding hydrides (11b-c, respectively) using two different hydride sources: 11a was formed by the reaction of with NaBH4 in refluxing THF, while 11b was synthesized in near quantitative yield using [Cp2ZrH2] in refluxing THF. Attempts to synthesize eta2-tetrafluorobenzyne complexes [Pt(L-L)(C6F4)] (L-L=dmpe, dcpe) from reaction of 11a-b with butyllithium were unsuccessful. The molecular structures of 3a,4a, 4c, 4d, 6b, 7a, 8, 11b and have been determined by X-ray crystallographic studies, and are discussed. 相似文献
A complete set of platinum(II) solketal substituted phthalocyanines has been synthesized and characterized. To evaluate their potential as Type II photosensitizers for photodynamic therapy, comparative studies of their photophysical and photochemical properties with analogous zinc(II) series have been achieved: electronic absorption, fluorescence quantum yields, lifetimes, and fluorescence quenching by benzoquinone, as well as singlet oxygen generation and photodegradation. It appears that platinum(II) phthalocyanines are worth being used as Type II photosensitizers, as they exhibit good singlet oxygen generation and appropriate photodegradation. 相似文献
The INDO–SCF method is used to provide electronic indices which are used as independent variables. These attempt to account for the variation in the antitumor activity and toxicity observed within a series of analogs of cis-diamino dichloro platinum(II). 相似文献
Several platinum(I1) complexes were subjected to mass spectrometric investigation. The major fragmentation pathways for dichloro-bis(phosphine) platinum(II) were elucidated to be: (i) successive loss of hydrogen chloride or chlorine depending on the structure of the phosphine, (ii) cleavage of P–R bond with the loss of R group, (iii) the presence of [R1R2R3P—Cl]+ in the mass spectra and (iv) fragmentation of the free phosphine. 相似文献
The reaction of 2 equiv of LiSeCC-n-C(5)H(11) (1) with cis-PtCl(2)(Ph(3)P)(2) (2) gives a mixture of the cis and trans isomers of Pt(Ph(3)P)(2)(SeCC-n-C(5)H(11))(2) (3), which slowly isomerizes in CH(2)Cl(2) to the preferred trans form trans-3. The closely related cis-[Pt(dppf)(2)(SeCC-n-C(5)H(11))(2)] (4) (dppf = bis(diphenylphosphino)ferrocene) was prepared by a similar metathetical reaction using the platinum chloride complex of the chelating dppf to impose the cis geometry. The structures of the cis and trans complexes have been investigated in solution by heteronuclear NMR ((31)P, (77)Se, and (195)Pt) and, in the cases of trans-3 and 4, characterized in the solid state by single-crystal X-ray diffraction. Changing the coordination geometry from cis to trans induces significant changes in the structural and spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands. 相似文献
PtIV and PdII complexes [Pt(L)2Cl2] and [Pd(HL)Cl2] [HL = salicyclaldehyde morpholine N-thiohydrazone (HL1), benzaldehyde morpholine N-thiohydrazone (HL2), acetophenone morpholine N-thiohydrazone (HL3), p-methylacetophenone morpholine N-thiohydrazone (HL4), cinnamaldehyde morpholine N-thiohydrazone (HL5), cyclohexanone morpholine N-thiohydrazone (HL6), benzaldehyde aniline N-thiohydrazone (HL7), benzaldehyde N-(methyl, cyclohexyl)-thiohydrazone (HL8) and benzaldehyde N-(ethyl, cyclohexyl)-thiohydrazone (HL9)] were prepared in MeOH and characterized by elemental analysis, i.r., electronic, 1H-n.m.r. and 13C-n.m.r. spectral data. For some of the complexes cyclic voltammetric and thermal studies were carried out. The in vitro antitumor activity of some complexes was measured. 相似文献
An in vivo study for determining the toxicity and efficacy of [Pt(S,S-dach)(phen)Cl(2).1.5H(2)O.0.5HCl (PHENSS) in female Specific Pathogen Free (SPF) Swiss nude mice bearing PC3 tumour xenografts revealed PHENSS to be non-toxic and effective in decreasing tumour growth. 相似文献
The electronic structures and spectroscopic properties of the three tridentate cyclometalated Pt(II) complexes Pt(N/\N/\C)C(triple bond)CPh (N/\N/\CH = 6-phenyl-2,2'-bipyridine) (1), Pt(N/\N/\S)C(triple bond)CPh (N/\N/\SH = 6-thienyl-2,2'-bipyridine) (2), and Pt(N/\N/\O)C(triple bond)CPh (N/\N/\OH = 6-furyl-2,2'-bipyridine) (3) were investigated theoretically using the density functional theory (DFT) method. The geometric structures of the complexes in the ground and excited states were explored at the B3LYP and UB3LYP levels, respectively. The absorption and emission spectra of the complexes in CH2Cl2 and CH3CN solutions were calculated by time-dependent density functional theory (TD-DFT) with the PCM solvent model. The calculated energies of the lowest singlet state and lowest triplet state in the three complexes are in good agreement with the results of experimental absorption and luminescence studies. All of the lowest-lying transitions were categorized as LLCT combined with MLCT transitions. The 623-nm emission of 1 from the 3A' --> 1A' transition was assigned as 3LLCT and 3MLCT transitions, whereas the 657- and 681-nm emissions of 2 and 3, respectively, were attributed to 3ILCT perturbed by 3MLCT transitions. NLO response calculations revealed that the nonzero values of the static first hyperpolarizability (beta0) for 1-3 are greatly enhanced through the introduction of the metal Pt(II) into the cyclometalated ligands, an effect that is determined by MLCT and LLCT transitions. 相似文献