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1.
Kaluđerović MR Kaluđerović GN Gómez-Ruiz S Paschke R Hemprich A Kühling J Remmerbach TW 《Journal of inorganic biochemistry》2011,105(2):164-170
Organogallium(III) dinuclear (1-9) and tetranuclear (10) complexes present potential therapeutic agents for the treatment of various types of cancer. The antiproliferative activity of 1-10 was evaluated with cell lines of head and neck squamous cell carcinomas, e.g. HN (soft palate), Cal27, Cal33 (tongue) and FaDu (hypopharynx) cell lines. The activity of compound 8 is comparable with that of cisplatin on cell line Cal27 (IC50 4.6 μM for both compounds). The mode of cell death induced, caspase activity and cell cycle analysis were evaluated for potential hit compounds 3, 5 and 8 Potential hit compounds 3, 5 and 8 were further evaluated for the mode of cell death, caspase activity and cell cycle analysis. Apoptosis induced by compounds 3, 5 and 8 on Cal27 and FaDu cells was confirmed by DNA laddering , as well as acridine orange (AO) and ethidium bromide (EB) double staining. These compounds (3, 5 and 8) induced caspase-independent apoptosis (within 4 h of action) in cell line Cal27. Extrinsic-mediated apoptosis associated with caspase 8 and 3 activation is the main mode of cytotoxicity induced on FaDu cells by compounds 3, 5 and 8. Cell cycle perturbations caused by these compounds are also observed. Our data suggest that compounds 3, 5 and 8 should be studied further for the treatment of head and neck cancer. 相似文献
2.
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
3.
Reactions of 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1), 2-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L2), 2-(3,5-di-tert-butylpyrazol-1-ylmethyl)pyridine (L3) and 2-(3-p-tolylpyrazol-1-ylmethyl)pyridine (L4) with K2[PtCl4] in a mixture of ethanol and water formed the dichloro platinum complexes [PtCl2(L1)] (1), [PtCl2(L2)] (2), [PtCl2(L3)] (3) and [PtCl2(L4)] (4). Complex 1, [PtCl2(L1)], could also be prepared in a mixture of acetone and water. Performing the reactions of L2 and L3 in a mixture of acetone and water, however, led to C-H activation of acetone under mild conditions to form the neutral acetonyl complexes [Pt(CH2COCH3)Cl(L2)] (2a) and [Pt(CH2COCH3)Cl(L3)] (3a). The same ligands reacted with HAuCl4 · 4H2O in a mixture of ethanol and water to form the gold salts [AuCl2(L1)][AuCl4] (5) [AuCl2(L2)][Cl] (6) [AuCl2(L3)][Cl] (7) and [AuCl2(L4)][AuCl4] (8); however, with the pyrazolyl unit in the para position of the pyridinyl ring in 4-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L5), 4-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L6) neutral gold complexes [AuCl3(L5)] (9) and [AuCl2(L6)] (10) were formed; signifying the role the position of the pyrazolyl group plays in product formation in the gold reactions. X-ray crystallographic structural determination of L6, 2, 33a, 8 and 10 were very important in confirming the structures of these compounds; particularly for 3a and 8 where the presence of the acetonyl group confirmed C-H activation and for 8 where the counter ion is . Cytotoxicity studies of L2, L4 and complexes 1-10 against HeLa cells showed the Au complexes were much less active than the Pt complexes. 相似文献
4.
Monoterpenoids (3 and 4), sesquiterpenoid (2), diterpenoid (1) and four phenethyl glucosides (5-8), together with fourteen known compounds, were isolated from the whole herb of Hyssopus cuspidatus. Their structures were determined by spectroscopic means. The abietane-type diterpenoids (1, 9, 10), rosmarinic acid (15) and salvigenin (17) inhibited leukotriene (LT) C4 secretion from primary alveolar cells of Wistar rats. 相似文献
5.
Rojalin Sahu 《Inorganica chimica acta》2010,363(7):1448-63
In air, hydrated ethanolic (95%) solution of 2-(aminomethyl) substituted pyridine and quinoline, on stirring with half equivalent of Cu(OAc)2·H2O, respectively afforded [Cu(bpca)(OAc)(H2O)]·H2O (1) and [Cu(bqca)(OAc)(H2O)] (2) {bpca = bis(2-pyridylcarbonyl)diimide ion and bqca = bis(2-quinolylcarbonyl)diimide ion} in good yields. These reactions involve oxidation of the methylene group and formation of the bond between nitrogen and carbon in N-C(O) through coupling. The complex [Cu(pqca)(OAc)(H2O)]3[Cu2(OAc)4(EtOH)2]1.5 (3) {pqca = (2-pyridylcarbonyl)(2-quinolylcarbonyl)diimide ion} was synthesized by stirring an ethanolic solution of the Schiff base [(2-pyridyl)-N-((2-quinolyl)methylene)methanamine] (L1) and with one equivalent of Cu(OAc)2·H2O. A plausible mechanism for the conversion has been proposed. The free ligands were isolated as crystalline solids from compounds 1-3, by extrusion of Cu2+ ion using EDTA2−. The molecular structures of 1-3 and bqcaH were established by X-ray crystallography and compounds having quinolyl group have π-stacking interactions. 相似文献
6.
Soo Hyun Kim Young Joo Song Hyo Geun Koo Jung In Poong Cheal Kim Sung-Jin Kim Youngmee Kim 《Inorganica chimica acta》2009,362(11):4119-202
Five polymeric metal(II)-benzoate complexes of formula [Mn(O2CPh)2(CH3OH)2(bpa)]n (1-Mn), [Co(O2CPh)2(H2O)(bpa)1.5]n (2-Co), [Ni(O2CPh)2(H2O)(bpa)1.5]n (3-Ni), [Cu(O2CPh)2(CH3OH)2(bpa)]n (4-Cu), and [Cd(O2CPh)2(bpa)1.5]n (6-Cd) have been synthesized and characterized (bpa = 1,2-bis(4-pyridyl)ethane). They showed two kinds of structures: parallelogram-like two-dimensional sheets for Co, Ni, and Cd, and one-dimensional chains for Mn, Cu, and Zn. Since similar structures provide similar coordination geometries, the structures depend on the coordination geometries of metal ions. The compounds 1-Mn, 2-Co, 4-Cu, 5-Zn, and 6-Cd have catalyzed efficiently the transesterification of a variety of esters, while 3-Ni has displayed a very slow conversion. The reactivity of catalyst 6-Cd containing Cd ion, well known as an inert metal ion for the ligand substitution, was found to be comparable to that of 5-Zn. The reactivities of the compounds used in this study are in the order of 5-Zn > 6-Cd > 1-Mn > 4-Cu > 2-Co ? 3-Ni, indicating that the non-redox metal-containing compounds (5-Zn and 6-Cd) show better activity than the redox-active metal-containing compounds (1-Mn, 4-Cu, 2-Co, and 3-Ni). 相似文献
7.
Chen ZF Mao L Liu LM Liu YC Peng Y Hong X Wang HH Liu HG Liang H 《Journal of inorganic biochemistry》2011,105(2):171-180
Three new compounds of Ga(III), Au(III), Sn(IV) with matrine (MT), [H-MT][GaCl4] (), [H-MT][AuCl4] () and [Sn(H-MT)Cl5] (), have been synthesized and characterized by elemental analysis, IR, ESI-MS and single crystal X-ray diffraction methods. The crystal structural analyses indicate that 1 and 2 are ionic compounds, whereas 3 is a tin(IV) complex formed by the monodentate MT via its carbonyl oxygen atom of MT coordinating to Sn(IV). Their in vitro cytotoxicity towards eight selected tumour cell lines has been evaluated by MTT (3-[4,5-Dimentylthiazole-2-yl]-2,5-diphenpyltetra-zolium bromide) method, and compounds 1 and 2 exhibit enhanced activity, such as 1 to SW480, 2 to HeLa, HepG2 and MCF-7, which exceeds matrine and cisplatin, and display synergistic contribution of their components. The cell cycle analyses show that compounds 1, 3 and MT exhibit cell cycle arrest at the G2/M phase. Interactions of these compounds with calf thymus DNA (ct-DNA) have been investigated by spectroscopic analyses. The planar extension of the intercalative metal-matrine compounds increases the interaction of the metal-matrine with DNA, indicating that the cationic metal ions and configuration of the intercalated metal-matrine will affect the extent of interaction. Compound 2, [H-MT][AuCl4], exhibits more intensive binding ability to DNA, which may correlate with intercalation and other action mode. The circular dichroism spectra of the ct-DNA bound with metal-MT compounds also suggest that ct-DNA interacted with 1, 2, 3 does not influence its secondary structure. Furthermore, both compounds 1 and 2 exhibit effective inhibition ability to topoisomerase (TOPO I) at concentration of 50 μM, while matrine and compound 3 do not. 相似文献
8.
A new easily synthetic route with a 96% yield of ligand 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethanol (L) is obtained. The reactivity of L against Pd(II), Zn(II) and Cu(II) leads to [PdCl2(L)2] (1), [ZnCl2(L)] (2) and [CuCl(L′)]2 (3) (L′ is the ligand L without alcoholic proton), respectively. According to the different geometries imposed by the metallic centre and the capability of L to present various coordination links, it has been obtained complexes with square planar (1 and 3) or tetrahedral (2) geometry and different nuclearity: monomeric (1 and 2) or dimeric (3). Complete characterisation by analytical and spectroscopic methods, resolution of L and 1-3 by single-crystal X-ray diffraction and magnetic studies for complex 3 are presented. 相似文献
9.
A series of organotin (IV) compounds of the type [R3SnL]2, R is Me (1), Bu (2), [R2SnL]2, R is Ph (3), Me (4), Bu (5), L is pyruvic acid thiophene-2-carboxylic hydrazone, and R2SnL, R is Me (6), Bu (7), Ph (8), L is salicylaldehyde thiophene-2-carboxylic hydrazone have been synthesized in 1:1 molar ratio. All compounds were characterized by elemental analysis, IR, 1H NMR, 13C NMR and 119Sn NMR spectra. The crystal structure of compounds 1, 3, 4, 8 have been determined by X-ray single crystal diffraction analyses, study found that the compounds 1 and 3 are rendered one-dimensional chain structure and the tin atoms are five-coordinated in a distorted trigonal-bipyramidal geometry. The compound 4 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. While the compound 8 is a monomer in which the tin atom adopts five-coordinated in distorted trigonal-bipyramidal geometry. 相似文献
10.
Nano-structures of two new Pb(II) coordination polymers, [Pb(DPAcO)2]n (1) and [Pb(MPAcO)2]n (2), HDPAcO = diphenyl acetic acid and HMPAcO = monophenyl acetic acid} were synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compound 2 was structurally characterized by single crystal X-ray diffraction. The crystal structure of the compound 2 consists of one-dimensional polymeric units of [Pb(MPAcO)2] and shows the coordination number in the PbII ions is six. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses and shows that nanostructures of compounds 1-2 are somewhat less stable then their bulk materials. PbO nano-powders were obtained by calcinations of the nano-structures of compounds 1 and 2 at 400 °C. 相似文献
11.
Lloyd T.J. Evans F. Geoffrey N. Cloke Peter B. Hitchcock 《Inorganica chimica acta》2010,363(6):1114-147
A series of mono- and bis-amide scandium and yttrium compounds incorporating the furyl-substituted disilazide ligand, [N{SiMe2R}2]− {i} (where R = 2-methylfuryl) have been synthesized. The compounds Sc{i}Cl2 (1), Sc{i}(CH2SiMe3)2 (2) and Sc{i}(OAr)2 (3) were made from suitable scandium starting materials employing either a salt metathesis protocol with Li{i} or via protonolysis of Sc-C bonds by the neutral amine H{i}. The thermally unstable bis-alkyl yttrium compound, ‘Y{i}(CH2SiMe3)2’ was isolated as the bis-THF adduct (4) and the bis-aryloxide Y{i}(OAr)2 (5) was synthesized by elimination of LiOAr from Y(OAr)3. The bis-amide complex Y{i}2Cl (6) and conversion to a rare example of an yttrium benzyl compound Y{i}2(CH2Ph) (7) are described. The yttrium cation, [Y{i}2]+, was synthesized by benzyl abstraction from 7 using B(C6F5)3. Structural characterization of representative examples show variation in the coordination modes for amide ligand {i}, differing primarily in the number of furyl groups that coordinate to the metal, with examples in which zero, one or two M-Ofuryl bonds are present. Preliminary investigation in two areas of catalysis are presented. 相似文献
12.
Dharamdat ChristendatIvor Wharf Anne-Marie LebuisIan S. Butler Denis F.R. Gilson 《Inorganica chimica acta》2002,329(1):36-44
A series of para-substituted triaryltin(pentacarbonyl)manganese(I) compounds [(p-XC6H4)3SnMn(CO)5: II, X=CH3; III, X=CH3O; IV, X=CH3S; V, X=F; VI, X=Cl; VII, X=CH3S(O2)] is reported for comparison with the known phenyl analogue I. IR data [ν(CO)] as well as complete 119Sn/55Mn/13C solution NMR results are given for I-VII. Chemical shifts, 119Sn versus 55Mn, except I, correlate well, but have differing single parameter (SP) correlations, 119Sn versus σI and 55Mn versus σ°p. These results are compared with previous SP studies of the 119Sn solution NMR spectra of the series, (p-XC6H4)4Sn and (p-XC6H4)3SnY (Y=Cl, Br, I). Full crystal structures are reported for compounds II-VI. All are similar to that of I, with the Mn(CO)5 moiety being a distorted tetragonal pyramid, and having a quasi-mirror plane through the central C4MnSnC3 skeleton. The Ar3Sn are distorted trigonal propellers with ring torsion angles in the range 30-80°, the exception being IV with one torsion angle of 22°. 相似文献
13.
The interaction of diethyl 2-pyridylmethylphosphonate (2-pmpe) ligand with CuX2 salts unexpectedly leads to the formation of compounds of the formula Cu(2-pca)2 [X=Cl− (1), CH3COO− (3)], and Cu(2-pca)Cl [X=Cl− (2)] (2-pca=pyridine-2-carboxylate ion). The diethyl 2-quinolylmethylphosphonate ligand (2-qmpe) reacts with CuX2 salts to similarly yield compounds of stoichiometry Cu(2-qca)2 · H2O (X=ClO4 − (4)], and for X=Cl Cu(2-qca)2 · H2O (5) and Cu(2-qca)Cl (6), (2-qca=quinoline-2-carboxylate ion). These compounds are products of a novel oxidative P-dealkylation reaction, which takes place on 2-pmpe and 2-qmpe ligands under the used conditions. The compounds were characterized by infrared, ligand field, EPR spectroscopy and magnetic studies. Cu(2-pca)2 exists in two crystalline forms, a blue form (1) and a violet form (3). For 3 the single-crystal structure was determined. The copper atom is four-coordinated in a square-planar geometry. The stack between related (and hence parallel) pca moieties involves interatomic distances of 3.27 Å. Cu(2-qca)2 · H2O also exists in two forms, a green (4) and a blue-green (5). Both these complexes are five coordinated, involve the same CuN2O3 chromophore and are examples of the distortion isomers. Variable-temperature magnetic susceptibility measurements (1.9-300 K) have shown that the antiferromagnetic coupling observed is much stronger in 6 than in 1, 3, 4 and 5. For 2 a ferromagnetic exchange occurs. 相似文献
14.
Bernadette S. Creaven Brian Duff Denise A. Egan Kevin Kavanagh Venkat Reddy Thangella Maureen Walsh 《Inorganica chimica acta》2010,363(14):4048-4058
The condensation of substituted aromatic aldehydes with 7-amino-4-methyl-quinolin-2(1H)-one (1) has lead to the isolation of quinolin-2(1H)-one derived Schiff bases (2-14). The copper(II) complexes (2a-14a) of the ligands were also prepared, and together with their corresponding free ligands were fully characterised by elemental analyses, spectral methods (IR, 1H and 13C NMR, AAS, UV-Vis), magnetic and conductance measurements. The bidentate ligands coordinated to the copper(II) ion through the deprotonated phenolic oxygen and the azomethine nitrogen of the ligands in almost all cases. X-ray crystal structures of two of the complexes, 5a and 8a, confirmed the bidentate coordination mode. All of the compounds were investigated for their antimicrobial activities against the fungus, Candida albicans, and against Gram-positive and Gram-negative bacteria. The compounds were found to have excellent anti-Candida activity but were inactive against Staphylococcus aureus and Escherichia coli. Selected compounds (2-8 and 2a-8a) were also screened for their in vitro anticancer potential using the human hepatic carcinoma cell line, Hep-G2. Several derivatives were shown to be active comparable to that of cisplatin. 相似文献
15.
Jan Moncol Barbora Kalinakova Miroslava Kleinova Daniela Hudecova Milan Mazur 《Inorganica chimica acta》2004,357(11):3211-3222
New copper(II) clofibriates (clof, {2-(4-chlorophenoxy)-2-methylpropionic or 2-(4-chlorophenoxy)isobutyric acid}) of composition Cu(clof)2L2 (where L=2-pyridylmethanol (2-pymeth) (1), N-methylnicotinamide (Menia) (4), N,N-diethylnicotinamide (Et2nia) (5), isonicotinamide (isonia) (7) or methyl-3-pyridylcarbamate (mpc) (8)), [Cu(clof)2(4-pymeth)2(H2O)] · 2H2O (4-pymeth=4-pyridylmethanol) (2 · 2H2O) and Cu(clof)2L (where L=4-pymeth (3) or Et2nia (6)) have been prepared and spectroscopically characterized. All the Cu(clof)2L2 compounds seem to possess distorted octahedral copper(II) stereochemistry with differing tetragonal distortions. An X-ray analysis of 1 was carried out and it featured a tetragonal-bipyramidal geometry around the copper(II) atom. X-ray analysis of 2 · 2H2O featured a square-pyramidal geometry around copper(II) atom. Both the Cu(clof)2L compounds seem to consist of a binuclear unit of tetracarboxylate type bridging. An X-ray analysis of 6 revealed typical binuclear paddle-wheel type structure, consisting of two copper(II) atoms in square-pyramidal geometry bridged by four carboxylate anions in the xy-plane. All complexes under study were characterized by EPR and electronic spectroscopy. The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi. 相似文献
16.
Schiff bases of 2-hydroxybenzophenone (HBP) (C6H5)(2-HOC6H4)CN(CH2)nEAr (L1/L2: E = S, Ar = Ph, n = 2/3; L3/L4: E = Se, Ar = Ph, n = 2/3; L5/L6: E = Te, Ar = 4-MeOC6H4, n = 2/3) and their complexes [PdCl(L-H)] (L = L1−L6; 1, 2, 3, 5, 7, 11), [PtCl(L3-H/L5-H)] (4/8), [PtCl2(L4/L6)2] (6/12), [(p-cymene)RuCl(L5/L6)]Cl (9/13) and [HgBr2(L5/L6)2] (10/14) have been synthesized and characterized by proton, carbon-13, selenium-77 and tellurium-125 NMR, IR and mass spectra. Single crystal structures of L1, 1, 3, 4, 5 and 7 were solved. The Pd-E bond distances (Å): 2.2563(6) (E = S), 2.3575(6)−2.392(2) (E = Se); 2.5117(5)−2.5198(5) (E = Te) are near the lower end of the bond length range known for them. The Pt-Se bond length, 2.3470(8) Å, is also closer to the short values reported so far. The Heck and Suzuki reaction were carried out using complexes 1, 3, 5 and 7 as catalysts under aerobic condition. The percentage yields for trans product in Heck reaction were found upto 85%. 相似文献
17.
Juan Guerrero Luis Cortez Liliana Farías Claudio Pettinari Francesco Caruso 《Inorganica chimica acta》2010,363(14):3809-3816
A series of [Cu(I)(2,2′-biquinoline)(L)](ClO4) complexes (L = bis(diphenylphosphino)methane (bppm), 1,2-bis(diphenylphosphino)ethane (bppe), 1,4-bis(diphenylphosphino)butane (bppb)) have been synthesized and characterized by elemental analysis, conductivity, ESI-mass, NMR and UV-Vis spectroscopies, cyclic voltammetry, X-ray diffraction ([Cu(I)(2,2′-biquinoline)(bppe)](ClO4)) and DFT calculations. These compounds are monometallic species in a distorted tetrahedral arrangement, in contrast with related compounds found as dinuclear according to diffraction studies. The spectroscopic properties are not directly correlated with the length of alkyl chain bridge between the bis-diphenylphosphine groups. In this way, the chemical shift of some 2,2′-biquinoline protons and the metal to ligand charge transfer (Cu to 2,2′-biquinoline) follows the order [Cu(2,2′-biquinoline)(bppm)](ClO4), [Cu(2,2′-biquinoline)(bppb)](ClO4), [Cu(2,2′-biquinoline)(bppe)](ClO4). The same dependence is followed by the potentials to Cu(II)/Cu(I) couple. These results are discussed in terms of inter-phosphorus alkane chain length and tetrahedral distortions on copper. 相似文献
18.
Marion Graf 《Inorganica chimica acta》2011,371(1):42-43
The synthesis of bis-cyclometalated aminocarboxylato complexes [M(α-aminocarboxylato)(ptpy)2] (M = Rh, 3, 4, 5; M = Ir, 6, 7, 8), ptpy = 2-(p-tolyl)pyridinato; aminocarboxylato = glycinato, l-alaninato, l-prolinato) from [{M(μ-Cl)(ptpy)2}2] (M = Rh, 1; M = Ir, 2) is described. The molecular structure of [Ir(l-alaninato)(ptpy)2] (7) was confirmed by a single-crystal X-ray diffraction study. Compound 7 crystallized from methanol-iso-hexane in the space group P21. For 7 the two diastereoisomers ΔIr, SC and ΛIr, SC were found crystallizing twice per unit. Absorption and emission spectra were recorded. The rhodium compounds are weak yellow-green and the iridium species strong green emitters. 相似文献
19.
Gerard A. van Albada Wen Tian Fu Ilpo Mutikainen Jan Reedijk 《Inorganica chimica acta》2009,362(12):4422-3393
Using the ligand 1,4,5-triazanaphthalene (abbreviated as tan) in combination with Cu(II) salts, three mononuclear compounds, Cu(tan)2Cl2 (1), Cu(tan)2Br2 (3), Cu(tan)2(NO3)2 (5) and three polynuclear compounds, [Cu(tan)Cl2]n (2), [Cu(tan)Br2]n (4), [Cu(tan)(NO3)2]n (6) have been synthesized and characterized by UV-Vis, EPR, FTIR and Far-FTIR spectroscopies. The crystal structures of compounds 1, 3, 5 and 6 are reported, as well as that of the dioxane adduct of compound 4, [Cu(tan)Br2(C4H8O2)](C4H8O2) (4A).The structure of (2) was solved by X-ray powder diffraction. The coordination geometry around the Cu(II) atoms is tetrahedral for (1) and (3), square-pyramidal for (4A) and distorted octahedral for (5) and (6). Magnetic susceptibility measurements on the polynuclear compounds revealed weak antiferromagnetic interactions between the Cu(II) atoms with interaction constants (J) of J = −9.1 and −10.5 cm−1, for 4 and 6, respectively. For compound 2 two options for possible interactions were considered, with interaction constants which vary for Jrung −22.0 to −13.5 cm−1 and Jrail −19.6 to −17.0 cm−1. These figures are discussed in the light of relevant structural parameters and literature. 相似文献
20.
Damián Fernández 《Inorganica chimica acta》2005,358(9):2575-2584
The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P3)Cl]Cl [P3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP3)Cl]Cl (5) (NP3 = tris[2-(diphenylphosphino)ethyl]amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the mononuclear heteroionic systems [M(L)Cl](CuCl2) [L = PNHP, M = Pd (1a); L = P3, M = Pd (2a), Pt (3a); L = NP3, M = Pt (5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P3 acting as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I) ion. However, the five-coordinate complexes [Pd(NP3)Cl]Cl (4), [M(PP3)Cl]Cl (M = Pd (6), Pt (7); PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6, 7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl3 [L = NP3, M = Pd (4a); L = PP3, M = Pd (6a), Pt (7a)] and ionic [MCu(PP3)Cl2](CuCl2) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by 31P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes 6b and 7b with ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former compounds. However, complexes [M(NP3)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function of the d8 metal centre. 相似文献