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1.
Solid complexes of lanthanide picrates with N-Ethyl-2-{2′-[(ethyl-phenyl-carbamoyl)-methoxy]-[1,1′]binaphthalenyl-2-yloxy}-N-phenyl-acetamide (L), [Ln(pic)3L] (Ln=La, Tb, Y), have been prepared and characterized by elemental analysis, IR and 1H NMR spectra. The molecular structure of [Tb(pic)3L] shows that the Tb(III) ion is nine-coordinated by four oxygen atoms from the L and five from two bidentate and one unidentate picrates. The complex forms a 1D supramolecular structure along z-axis.  相似文献   

2.
Reactions of triphenyltin chloride or isothiocyanate with lactum yield complexes of the type Ph3SnX · L (X = Cl or NCS, L = lactam). The coordination of the carbonyl group of lactams to the tin atom has been suggested by IR data and confirmed by X-ray diffraction analysis.The crystal and molecular structure of triphenyltin chloride-ϵ-caprolactam complex, C24H26ClNOSn, has been determined by X-ray diffraction analysis. The crystals are orthorhombic, space group Pbca, a 18.839(1), b 14.392(2), c 29.059(6) Å, Z = 8; R = 0.047, Rw = 0.058 for 3579 unique reflections. The geometry around the tin atom is trigonal bipyramidal with the three phenyl groups defining the equatorial plane and a chlorine ion and a carbonyl oxygen of the caprolactam ligand occupying the axial positions.  相似文献   

3.
A series of heteroleptic scandium SALEN complexes, [(SALEN)Sc(mu-Cl)]2 and (SALEN)Sc[N(SiHMe2)2] is obtained via amine elimination reactions using [Sc(N(i)Pr2)2(mu-Cl)(THF)]2 and Sc[N(SiHMe2)2]3(THF) as metal precursors, respectively. H(2)SALEN ligand precursors comprising H2Salen [(1,2-ethandiyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol], H2Salpren [(2,2-dimethylpropanediyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol], H2Salcyc [(1R,2R)-(-)-1,2-cyclohexanediyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol] and H2Salphen [((1S,2S)-(-)-1,2-diphenylethandiyl)bis(nitrilomethylidyne)bis(2,4-di-tert-butyl)phenol] are selected according to solubility and ligand backbone variation ("=N-(R)-N=" bite angle) criteria. Consideration is given to the feasibility of [Cl --> NR2] and [N(SiHMe2)2--> OSiR3] secondary ligand exchange reactions. X-ray crystal structure analyses of donor-free (Salpren)Sc(N(i)Pr2), (R,R)-(Salcyc)Sc[N(SiHMe2)2], (Salen)Sc(OSi(t)BuPh2) and (Salphen)Sc(OSiH(t)Bu2) reveal (i) a very short Sc-N bond distance of 2.000(3) A, (ii) weak beta(Si-H)(amido)-Sc agostic interactions and (iii) an exclusive intramolecularly tetradentate and intrinsically bent coordination mode of the SALEN ligands with angle(Ph,Ph) dihedral angles and Sc-[N(2)O(2)] distances in the 124.27(9)-127.7(3) degrees and 0.638(1)-0.688(1) A range, respectively.  相似文献   

4.
Xu G  Wang ZM  He Z  Lü Z  Liao CS  Yan CH 《Inorganic chemistry》2002,41(25):6802-6807
A series of nonanuclear lanthanide oxo-hydroxo complexes of the general formula [Ln(9)(mu(4)-O)(2)(mu(3)-OH)(8)(mu-BA)(8)(BA)(8)](-)[HN(CH(2)CH(3))(3)](+).(CH(3)OH)(2)(CHCl(3)) (BA = benzoylacetone; Ln = Sm, 1; Eu, 2; Gd, 3; Dy, 4; Er, 5) were prepared by the reaction of hydrous lanthanide trichlorides with benzoylacetone in the presence of triethylamine in methanol and recrystallized from chloroform/methanol (1:10) at room temperature. These five compounds are isomorphous. Crystal data for 1: cubic, Pn3n; T = 180 K; a = 33.8652(4) A; V = 38838.4(8) A(3); Z = 6; D(calcd) = 1.125 g cm(-)(3); R1 = 3.37%. Crystal data for 2: cubic, Pn3n; T = 180 K; a = 33.8252(8) A; V = 38700.9(16) A(3); Z = 6; D(calcd) = 1.133 g cm(-)(3); R1 = 4.97%. Crystal data for 3: cubic, Pn3n; T = 180 K; a = 33.7061(6) A; V = 38293.5(12) A(3); Z = 6; D(calcd) = 1.157 g cm(-)(3); R1 = 5.13%. Crystal data for 4: cubic, Pn3n; T = 180 K; a = 33.5900(7) A; V = 37899.2(14) A(3); Z = 6; D(calcd) = 1.182 g cm(-)(3); R1 = 4.03%. Crystal data for 5: cubic, Pn3n; T = 180 K; a = 33.5054(8) A; V = 37613.6(16) A(3); Z = 6; D(calcd) = 1.202 g cm(-)(3); R1 = 4.86%. The core of the anionic cluster comprises two vertex-sharing square-pyramidal [Ln(5)(mu(4)-O)(mu(3)-OH)(4)](9+) units. The compounds were characterized by elemental analysis, IR, fast atom bombardment mass spectra, thermogravimetry, and differential scanning calorimetry. The thermal analysis indicated that the nonanuclear species were stable up to 150 degrees C. Luminescence spectra of 2 and magnetic properties of 1-5 were also studied.  相似文献   

5.
Two copper complexes with long rigid ligands, Cu(Tta)2(L1) (I), and Cu(Tta)2(L2) (II), where L1 = (E)-3-(4-(1H-benzo[d]imidazol-1-yl)-(4-phenyl)phenyl)-1-phenylprop-2-en-1-one, L2 = (E)-3-(4-(1H-imidazol-1-yl)phenyl)-1-(4-phenyl)phenyl)prop-2-en-1-one), have been synthesized and characterized. The single-crystal X-ray analysis (CIF files CCDC nos. 1409671 (I) and 1409672 (II)) for complexes I and II demonstrates that each copper ion assumes a distorted square-pyramidal MO4N polyhedron in which four oxygen atoms come from the Tta ligands, and one nitrogen atom comes from the N-donor ligand. Both of the complexes are linked into 3D networks through weak intermolecular interactions.  相似文献   

6.
Treatment of [RuCl2(PPh3)3] with 2 equiv. HimtMPh (HimtMPh?=?1-(4-methyl-phenyl)-imidazole-2-thione) in the presence of MeONa afforded cis-[Ru(κ 2-S,N-imtMPh)2(PPh3)2] (1), while interaction of [RuCl2(PPh3)3] and 2 equiv. HimtMPh in tetrahydrofuran (THF) without base gave [RuCl2(κ 1-S-HimtMPh)2(PPh3)2] (2). Treatment of [RuHCl(CO)(PPh3)3] with 1 equiv. HimtMPh in THF gave [RuHCl(κ 1-S-HimtMPh)(CO)(PPh3)2] (3), whereas reaction of [RuHCl(CO)(PPh3)3] with 1 equiv. of the deprotonated [imtMPh]? or [imtNPh]? (imtNPh?=?1-(4-nitro-phenyl)-2-mercaptoimidazolyl) gave [RuH(κ 2-S,N-imtRPh)(CO)(PPh3)2] (R?=?M 4a, R?=?N 4b). The ruthenium hydride complexes 4a and 4b easily convert to their corresponding ruthenium chloride complexes [RuCl(κ 2-S,N-imtMPh)(CO)(PPh3)2] (5a) and [RuCl(κ 2-S,N-imtNPh)(CO)(PPh3)2] (5b), respectively, in refluxing CHCl3 by chloride substitution of the RuH. Photolysis of 5a in CHCl3 at room temperature afforded an oxidized product [RuCl2(κ 2-S,N-imtMPh)(PPh3)2] (6). Reaction of 6 with excess [imtMPh]? afforded 1. The molecular structures of 1·EtOH, 3·C6H14, 4b·0.25CH3COCH3, and 6·2CH2Cl2 have been determined by single-crystal X-ray crystallography.  相似文献   

7.
The reaction of the ambidentate ligand 2-(3,4-dichlorophenyl)imino-N-(2-thiazin-2-yl)thiazolidine (TdTz) with CuCl2·2H2O results in the formation of two new copper complexes, which has been characterized in the solid state by elemental analysis, UV-Vis-NIR diffuse reflectance, electron paramagnetic resonance (EPR) spectroscopy, magnetic measurements, infrared spectroscopy and X-ray powder diffraction. These studies have revealed that the two copper complexes are linkage isomers, which the metal atom is four-coordinated by two chloride ions and one ligand TdTz that act as a N,N bidentate ligand in one case and as a N,S bidentate ligand in the other one.  相似文献   

8.
The first phosphinooxazoline chelate complexes of iron were synthesized, and their structural and electronic properties were studied.The known phosphinooxazolines 2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole (7a), 2-(2-(diphenylphosphino)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7b), (S)-4-benzyl-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole (7e) and (R)-2-(2-(diphenylphosphino)phenyl)-4-phenyl-4,5-dihydrooxazole (7f) were synthesized by a modified three step literature procedure with improved 67-60% overall yields. The new electronically tuned phosphinooxazolines 2-(5-bromo-2-(diphenylphosphino)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7c), 3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-(diphenylphosphino)-N,N-dimethylaniline (7d) and 2-(2-(diphenylphosphino)-3-(trifluoromethyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7g) were synthesized in three to six steps with 59-29% overall yields. Reaction of 7a-f with CpFe(CO)2I (110 °C, 2 h, toluene) gave the iodide salts of the new iron phosphinooxazoline complexes [CpFe(CO)(7a-f)]+ in 87-21% yield. The new complexes were characterized by X-ray and the molecular structures confirm the octahedral coordination geometry and the half-sandwich structure about the iron center. The impact of different oxazoline ligands on the steric and electronic properties of their iron complexes was determined by analysis of selected bond lengths, νCO stretching frequency and the oxidation potentials of the ligands and the iron complexes.  相似文献   

9.
10.
Highly crosslinked polymeric networks formed by cyclodextrins (CD) have recently been shown to be highly versatile nanosponge systems, being for instance very efficient both for drug delivery and for pollutants removal. Here we report some molecular simulation results for dry and hydrated CD nanosponge models aimed to study their swelling behavior. We also report simulation results about the water mobility in these systems in terms of the calculated diffusion coefficient of “free” and of “bound” water molecules confined within the nanosponge cavities. Furthermore, we also suggest the presence of surface-constrained water molecules temporarily bound to the network surface but eventually set free in the bulk.  相似文献   

11.
We have synthesized a series of trinuclear gold(I) complexes, namely, [Au3(mu-dpmp)(S2CNR2)nCl3-n] (n = 0-3; R = Me, CH2Ph), [Au3(mu-dpmp)(mu-S2CNR2)Cl](CF3SO3) (R = Me, CH2Ph), and [Au3(mu-dpmp)(mu-S2CNMe2)(C6F5)]X (X = Cl, CF3SO3), containing the triphosphine dpmp [bis(diphenylphosphinomethyl)phenylphosphine] and varying amounts of dithiocarbamate. NMR experiments show fluxional behavior in solution for most of these derivatives because several arrangements of the ligands are possible. The crystal structure of [(mu-dpmp)(AuCl)3] has been determined by X-ray diffraction studies; the molecule displays mirror symmetry and involves an angular arrangement of the gold atoms [Au-Au-Au 119.603(14) degrees, Au-Au 3.3709(4) A]. We have studied the optical properties of these derivatives in the solid state, finding a red shift as a function of the dithiocarbamate number and, for some derivatives, wavelength-dependent emission spectra at low temperature.  相似文献   

12.
Treatment of cyclotrisilathiane (Me2SiS)3 with 3 equiv. of RLi (R = Me, But) in hexane-Et2O afforded the lithium silanethiolates LiSSiMe2R, and the tmeda adduct [(tmeda)LiSSiMe2But]2 1 (tmeda =N,N,N',N'-tetramethylethylenediamine) was isolated in the case of R = But. Reaction of Fe(CH3CN)2(CF3SO3)2, CoCl2, and [Cu(CH3CN)4](PF6) with 1 gave rise to the silanethiolato complexes M(SSiMe2But)2(tmeda)(M = Fe 2, Co 3), and [Cu(SSiMe2But)]4 4, respectively. Complexes (C5H5)2Ti(SSiMe2R)2(R = Me 5, But 6) and Ni(SSiMe2R)2(dppe)[R = Me 7, But 8; dppe = 1,2-bis(diphenylphosphino)ethane] were prepared from treatments of (C5H5)2TiCl2 and NiCl2(dppe) with the corresponding lithium silanethiolates. Complex 7 readily reacted with (C5H5)TiCl3 to produce the Ti-Ni heterobimetallic compound (C5H5)TiCl(mu-S)2Ni(dppe) 9, in which silicon-sulfur bond cleavage took place. Characterization of all compounds through spectroscopic techniques and elemental analyses are also described. X-Ray structural data for compounds 1 and 3-9 are reported.  相似文献   

13.
Treatment of [Cp*Ru(dppe)]+ with B-triethynyl-N-trimethylborazine and piperidine produces the trimetallic complex [Cp*Ru(dppe)(CC)]3B3N3Me3, the structure of which has been confirmed by X-ray diffraction. Reaction of RuHCl(CO)(PPh3)3 with B-triethynyl-N-trimethylborazine produces the trimetallic complex [RuCl(CO)(PPh3)2(CH=CH)]3B3N3Me3.  相似文献   

14.
Yang CT  Li Y  Liu S 《Inorganic chemistry》2007,46(21):8988-8997
To understand the coordination chemistry of a DO3A-conjugated triphenylphosphonium (TPP) cation, triphenyl(4-((4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-1-yl)methyl)benzyl)phosphonium (DO3A-xy-TPP), with diagnostically important metal ions, In(DO3A-xy-TPP)+, Ga(DO3A-xy-TPP)+, and Mn(DO3A-xy-TPP) were prepared by reacting DO3A-xy-TPP with 1 equiv of the respective metal salt. All three complexes have been characterized by elemental analysis, IR, ESI-MS, NMR methods (for In(DO3A-xy-TPP)+ and Ga(DO3A-xy-TPP)+), and X-ray crystallography. Results from HPLC concordance experiments show that (111)In(DO3A-xy-TPP)+ and In(DO3A-xy-TPP)+ have the same composition. The solid-state structures of In(DO3A-xy-TPP)+ and Mn(DO3A-xy-TPP) are very similar with DO3A being heptadentate in bonding to In(III) and Mn(II) in a monocapped octahedral coordination geometry. Because of the smaller size of Ga(III), the DO3A in Ga(DO3A-xy-TPP)+ is only hexadentate with four amine-N and two carboxylate-O atoms bonding to Ga(III). One carboxylic acid group in DO3A is deprotonated to balance the positive charge of Ga(III). The coordination geometry of Ga(DO3A-xy-TPP)+ is best described as a distorted octahedron. The NMR data shows that the coordinated DO3A in In(DO3A-xy-TPP)+ and Ga(DO3A-xy-TPP)+ is symmetrical in aqueous solution. There is no dissociation of the acetate chelating arms in In(DO3A-xy-TPP)+ and Ga(DO3A-xy-TPP)+, providing indirect evidence for the high solution stability of (111)In(DO3A-xy-TPP)+ and (68)Ga(DO3A-xy-TPP)+.  相似文献   

15.
The orthometalated complex [Pd(μ-Cl)(C6H5C6H4C(O)CHPPh2C6H42-C,C)]2 (1) was prepared by refluxing in MeOH/CH2Cl2 equimolecular amounts of Pd(OAc)2 and (Ph)3PCHCOC6H4-Ph-4 (=PhBPPY) followed by addition of excess NaCl. Complex 1 reacts with 4-picoline to give the mononuclear derivative [Pd(PhC6H4COCHPPh2C6H4)(4-picoline)] (2) whose crystal structure has been determined by X-ray diffraction. The precursor complex (1) could not be isolated in a pure form, but it can be used as a starting material for the synthesis of derivatives of mononuclear cyclo-palladated complexes. Orthometallation and ylide C-coordination in complexes 35 were characterized by elemental analysis as well as various spectroscopic techniques.  相似文献   

16.
A series of novel polyiron species have been prepared from the reaction of iron chloride with the 2,5-disubstituted pyridines H2L(n) (H2L1) = N,N'-bis(n-butylcarbamoyl)pyridine-2,6-dicarboxamide; H2L2 = N,N'-bis(n-ethylcarbamoyl)pyridine-2,6-dicarboxamide). By small modifications of the experimental conditions under which the reactions are carried out, it has been possible to prepare the quadruply stranded diiron(II) complex [Fe2(mu-H2L1)4(mu-Cl)2][FeCl4]2 (1), the metallamacrocycle [Fe2(mu-H2L1)2(THF)4Cl2][FeCl4]2 (2), the hexairon(III) compound [Fe6(L1)2(mu-OMe)6(mu4-O)2Cl4] (3), and the mixed-valence trinuclear iron complexes [Fe3(L(n))3(mu3-O)] (n = 1, 4; n = 2, 5). The X-ray crystal structures of 3 and 5 and magnetic studies for all the compounds are herein presented. Interestingly, the structural analysis of 5 at room temperature indicates that one of the iron centers is Fe(III) while the other two have an average valence state between Fe(II) and Fe(III). The five complexes herein presented demonstrate the great versatility that the new ligand has as a building block for the formation of supramolecular coordination assemblies.  相似文献   

17.
《Polyhedron》2002,21(5-6):619-627
The first guanidinate complexes of tin have been prepared using N,N′,N′′-trialkylguanidinates ([(RN)2C(NRH)]; R=cyclohexyl; isopropyl) and 1,3,4,6,7,8-hexahydro-2H-pyramido[1,2-a]pyramidinate (hpp) as ligands. The direct reaction between triisopropylguanidine and SnCl4 provided the complex {[iPrN]2C[NHiPr]}SnCl3 (1) along with concomitant formation of the guanidinium salt {C[NHiPr]3}+[SnCl5(THF)] (2). The Sn(II) guanidinate complexes {(C6H11N)2C[NH(C6H11)]}2Sn (3) and {CN[N(CH2)3]2}2Sn (4) were prepared through metathesis reactions between 0.5 equiv. SnCl2 and (C6H11N)2C[NH(C6H11)]Li or hppLi, respectively. Complex 4 is the first reported mononuclear complex of this ligand. In contrast, the reaction of hppLi with 1 equiv. SnCl2 afforded a bridging dinuclear species, {CN[N(CH2)3]2SnCl}2 (5). A second mononuclear complex of the hpp ligand, {CN[N(CH2)3]2}2SnCl2 (6), was the product obtained from the reaction of 2 equiv. of hppLi with SnCl4. The full structural details of compounds 1 and 36 are reported. In the case of compounds 1 and 3 these results revealed a distinctly unsymmetrical bonding mode for the bidentate guanidinate ligand and suggest variable degrees of π delocalization with the ligand. The geometries of the Sn centers in 3, 4 are derived from distorted trigonal bipyramidal coordination with a stereochemically active lone pair occupying one coordination site. In contrast, complex 5 displayed a geometry derived from a tetrahedral ligand array with one vertex occupied by a lone pair of electrons. Complex 6 is six coordinate and possesses 2 equiv. chelating bidentate hpp ligands and two cis-chloro groups.  相似文献   

18.
The synthetic, thermodynamic and structural investigations of organoruthenium complexes of the form Cp*Ru(triene)OTf (Cp*=n5-(CH3)5C5; triene=anisole 1, indole 2, cycloheptatriene 3, OTf=OSO2CF3) are presented in this contribution. A direct entryway into the thermochemistry of these complexes is made possible by the rapid and quantitative arene/triene substitution for the three acetonitrile ligands in Cp*Ru(CH3CN)3OTf. The solution calorimetric study establishes the following order of stability: cycloheptatriene < anisole < indole. This study helps clarify the enthalpic and entropic components to the thermodynamic driving forces behind the formation of ruthenium arene/triene complexes. The solid-state structures of these three complexes(1–3) were determined by X-ray single-crystal studies. Thermodynamic factors affecting the Ru-triene bond energy are compared with structural results for these three ruthenium complexes.  相似文献   

19.
Mixed carbene-carboxylate complexes of Palladium(II) have been prepared by reacting {1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidene} palladium(II) diiodide (1) [Angew. Chem. 107 (1995) 2602; Angew. Chem. Int. Ed. Engl. 34 (1995) 2371; J. Organomet. Chem. 557 (1998) 93] with AgO2CR, where R=CF3, CF2CF3 and CF2CF2CF3. In this manner, {1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidene} palladium(II) bis(trifluo-roacetate) (2), {1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidene} palladium(II) bis(pentafluoropropionate) (3) and {1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidene} palladium(II) bis(heptafluorobutyrate) (4) were obtained. All three complexes were fully characterized by 1H-, 13C- and 19F NMR spectroscopy as well as ESI mass spectrometry. X-ray crystal structure analyses of complexes 3 and 4 reveal mononuclear species with a square planar metal center coordinated by a cis-chelating dicarbene and two monodentate carboxylate ligands. The results show that the introduction of a cis-chelating N,N-heterocyclic carbene ligand stabilizes the palladium-carboxylate moiety effectively.  相似文献   

20.
We have successfully synthesized new oxovanadium (IV) complexes with dimedone derivatives and their structure were confirmed by elemental analyses, spectroscopic techniques (FT-IR, UV–visible, EPR) and thermal analysis. The reaction of [VO (acac)2] with the azo dimedone ligands ( HL n ) produced mononuclear oxovanadium (IV) complexes with formula [VO (Ln)2]H2O. Results of the molar conductance proved that VO2+ complexes are non-electrolytes and fall in the range 14–16 Ω-1cm2mol−1. The coordination geometry of VO (IV) complexes is square-pyramidal, where vanadium (IV) ion is coordinated by oxygen atom of the carbonyl (C=O) group, and nitrogen atom of the deprotonating hydrazone moiety (–NH–), while the fifth position is occupied by an oxo group. Moreover, the optimized structure, bond angles, bond lengths, as well as the calculated quantum chemical parameters of the complexes have been estimated. DNA binding activities of the complexes were investigated using electronic absorption titration and viscosity measurements. The obtained results showed groove binding of the complexes to CT-DNA accompanied with a partial insertion of the ligand between the base stacks of the DNA with a binding constant of 2.07–5.51 x 105 M−1 range. Evaluation results of the synthesized complexes against the human cancer cell lines HepG-2 and MCF-7, as compared to the positive controls in the viability assay of vinblastine and colchicine have been reported. The in vitro anti-oxidant activity of all the complexes is determined by DPPH free radical-scavenging assay. Finally, the anti-microbial activities of the complexes have been investigated against fungal (Candida albicans), gram negative bacteria (Escherichia coli), and gram positive bacteria (Staphylococcus aureus) using the disc-diffusion method.  相似文献   

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