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1.
The thiocarbamates 4-RC6H4NHC(S)NR2′ (R = H, Cl; R′ = Me, Et), 4-ClC6H4NHC(S)NR (NR = 2-pyridylpiperazine) react with cis-[PtCl2(PTA)2] (PTA = 1,3,5-triaza-7-phosphaadamantane) in the presence of base to afford the monocationic platinum(II) complexes cis-[Pt{SC(NR2′) = NC6H4R}(PTA)2]+ (R = H, Cl; R′ = Me, Et), cis-[Pt{SC(NR) = NC6H4Cl}(PTA)2]+ (NR = 2-pyridylpiperazine), which were isolated as their PF6 salts in high yields. The complexes were fully characterised spectroscopically and also by X-ray crystallography. Cytotoxicity of these complexes was studied in vitro in three human cancer cell lines (CH1, A549 and SW480) using the MTT assay.  相似文献   

2.
The reaction of imidoyl chlorides [V(NR)Cl3] (R = Ph 1, Tol 2, tBu 3) and calix[4]arene methyl ether H3Mecalix unexpectedly leads to the formation of the structurally characterized vanadium (IV) complex [VCl(Mecalix)] (4). Calix[4]arene methyl ether stabilized imido complexes of the type [V(NR)(Mecalix)] (R = Ph 7, Tol 8, tBu 9) were afforded from the reaction of [V(NR)Cl3] (R = Ph 1, Tol 2, tBu 3) and the tris(lithium) or tris(sodium) salt of the calix[4]arene ether. The lithium salt [{Li3(Mecalix)}2] (5) is a dimer in the solid state, in which two monomeric trianions are bridged by lithium cations. Imido complexes [M(NR)(Mecalix)] (M = Nb: R = tBu, 12, R = Tol 13, R = Mes 14, R = Dipp 15; M = Ta: R = tBu 16, R = Tol 17) (Tol = 4-C6H4Me, Mes = 2,6-C6H3Me2; Dipp = 2,6-C6H3iPr2) have been prepared from structurally characterized [NbCl2(Mecalix)] (10) and previously known [TaCl2(Mecalix)] (11) via reaction with two equivalents of the appropriately metallated (Li, K) primary amine. The molecular structures of 13 and 15 confirm the mononuclear nature of these complexes.  相似文献   

3.
Transmetallation reactions of ortho-mercurated iminophosphoranes (2-ClHgC6H4)Ph2PNR with [AuCl4] gives new cycloaurated iminophosphorane complexes of gold(III) (2-Cl2AuC6H4)Ph2PNR [R = (R,S)- or (S)-CHMePh, p-C6H4F, tBu], characterised by NMR and IR spectroscopies, ESI mass spectrometry and an X-ray structure determination on the chiral derivative R = (S)-CHMePh. The chloride ligands of these complexes can be readily replaced by the chelating ligands thiosalicylate and catecholate; the resulting derivatives show markedly higher anti-tumour activity versus P388 murine leukaemia cells compared to the parent chloride complexes. Reaction of (2-Cl2AuC6H4)Ph2PNPh with PPh3 results in displacement of a chloride ligand giving the cationic complex [(2-Cl(PPh3)AuC6H4)Ph2PNPh]+, indicating that the PN donor is strongly bonded to the gold centre.  相似文献   

4.
Eight triorganotin complexes of the types [(R3Sn)2(C24H16N8S2)].Y (R = Ph, Y = 0 (1); R = PhCH2, Y = 2CH3OH (2); R = n-Bu, Y = 0 (3)), [(R3Sn)2(C24H16N8S2)]n (R = Me (4)), [(R3Sn)2(C12H6N6S4)] · Y (R = Ph, Y = CH2Cl2 (5); R = PhCH2, Y = 0 (6)) and [(R3Sn)2(C12H6N6S4)] (R = Bu (7), R = Me (8)) have been obtained by H2L1 (H2L1 derived from 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol) and H2L2 (H2L2 derived from 5-amino-1,3,4-thiadiazole-2-thiol) with triorganotin chloride in the presence of sodium ethoxide. All the complexes were characterized by elemental, IR and NMR spectra analyses, except for complexes 1, 3, 6 and 8, other complexes were also characterized by X-ray diffraction analyses, which reveal that complexes 2 and 5 are dinuclear structures, complex 4 has a 2D network structure and complex 7 forms a macrocyclic structure linked by intermolecular N → Sn interactions.  相似文献   

5.
A series of pyrazolyl palladium(II), platinum(II) and gold(III) complexes, [PdCl2(3,5-R2bpza)] {R = H (1), R = Me (2), bpza = bis-pyrazolyl acetic acid}, [PtCl2(3,5-R2bpza)] {R = H (3a), R = Me (4)}, [AuCl2(3,5-R2bpza)]Cl {R = H (5a), R = Me (6a)} and [PdCl2(3,5-R2bpzate)] {R = Me (7)} have been synthesised and structurally characterised. Single crystal X-ray crystallography showed that the pyrazolyl ligands exhibit N^N-coordination with the metals. Anticancer activities of six complexes 1-6a were investigated against CHO cells and were found to have low activities. Substitution reactions of selected complexes 1, 2, 3a and 5a with l-cysteine show that the low anticancer activities compounds and that the rate of substitution with sulfur-containing compounds is not the cause of the low anticancer activities.  相似文献   

6.
The thermal reaction of Ru3(CO)12 with various carboxylic acids (benzoic, 4-hydroxyphenylacetic, ferrocenic, stearic, oleic, 4-(octadecyloxy)benzoic) in refluxing tetrahydrofuran, followed by addition of 5-(4-pyridyl)-10,15,20-triphenylporphyrin (L), gives the dinuclear complexes Ru2(CO)4(OOCR)2L2 (1: R = -C6H5, 2: R = -CH2-p-C6H4OH, 3: R = -C5H4FeC5H5, 4: R = -(CH2)16CH3, 5: R = -(CH2)7CHCH(CH2)7CH3, 6: R = -p-C6H4O(CH2)17CH3). Complexes 1-6 were characterised by IR, NMR, and ESI-MS as well as by elemental analysis. The UV-Vis spectra show the Soret band centred at 417 nm and the Q bands at 515, 550, 590 and 645 nm, respectively.  相似文献   

7.
The new aryl phosphinites PPh2OR (R = 2,4,6-Me3C6H2, 1; R = 2,6-Ph2C6H3, 2) have been prepared from chlorodiphenylphosphine and the corresponding phenols. In these ligands, the ortho-positions of the aromatic phosphite function are blocked by methyl and phenyl substituents, which allows coordination to metal centres without ortho-metallation. Thus, reaction with [PdCl2(cod)] leads to the complexes trans-[PdCl2(PPh2OR)2] (R = 2,4,6-Me3C6H2, 3; R = 2,6-Ph2C6H3, 4), while the reaction with [Rh2(CO)4Cl2] gives trans-[Rh(CO)Cl(PPh2OR)2] (R = 2,4,6-Me3C6H2, 5; R = 2,6-Ph2C6H3, 6). The single-crystal X-ray structure analyses of 3 and 5 confirm the trans-coordination of the new ligands in these square-planar complexes.  相似文献   

8.
Reactions of H[AuCl4] with N-substituted 2-pyridine thiocarboxamide ligands 2-(C5H4N)C(S)NHR (R = p-C6H4Me, CH2Ph, Me, p-C6H4OMe) gave cycloaurated derivatives {(C5H4N)C(S)NR}AuCl2, with the ligand bonded as the thiol tautomer through the deprotonated SH group and the pyridine N atom to give a five-membered metallacyclic ring. The X-ray structure determination of the R = CH2Ph derivative shows a square-planar gold(III) complex that dimerises in the solid state by weak Au···S intermolecular interactions. In contrast, in the reaction of H[AuCl4] with 2-(C5H4N)C(S)NHR where R = 2-pyridyl, the ligand was oxidised to give a 1,2,4-thiadiazolo[2,3-a]pyridinium heterocyclic ring that was crystallographically characterised.  相似文献   

9.
A new series of biscyclometalated dinuclear rhodium (II) compounds with the general formula Rh2(O2CR)2(PC)2 · 2H2O, being PC = (C6H4)P(C6H5)2, R = CH3 (1 · 2H2O), PC = [(p-CH3 OC6H3)P(p-CH3 OC6H4)2], R = CF3 (2 · 2H2O), PC = (C6H4)P[CH(CH3)2]2, R = CH3 (3 · 2H2O) and PC = (C6H4)P(C6H5)2, R = C6F5 (4 · 2H2O) has been obtained. The crystal structures for these compounds have been determined by X-ray diffraction and the main structural trends, bond lengths, bond angles and torsion angles have been analyzed, and have also been compared with the structural parameters for different analogous complexes described previously in the literature.  相似文献   

10.
Complexes cis,trans-Fe(CO)2(PMe3)2RR′ (R = CH3, R′ = Ph (2); R = CH3, R′ = CHCH2 (3); R = CHCH2, R′ = Ph (4); R = R′ = CHCH2 (5); R = R′ = CH3 (6)) were prepared by reaction of cis,trans-Fe(CO)2(PMe3)2RCl (1) with organolithium reagents LiR′. All complexes were characterized in solution by IR and 1H, 31P and, in a few cases, 13C NMR mono- and bi-dimensional spectroscopies. Complexes 5 and 6 were structurally characterized by X-ray diffractometric methods. In solution complexes 2, 3 and 4 undergo slowly coupling of the σ-hydrocarbyl substituents leading to Fe(CO)3(PMe3)2 and other decomposition products. Complex 6 was very stable in solution in the absence of nucleophiles and in the solid state. Complex 5 transformed through intramolecular coupling of the vinyl groups into Fe(CO)(PMe3)24-butadiene) (7), which was characterized in solution by IR and NMR spectroscopies.  相似文献   

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