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1.
The monomeric cobalt-phosphite-thiolato complex [ Co (mpt)2 {P (OCH3 )3 }2 ] BF4 (Hmpt = 2-mercaptothiazoline) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the monoclinic space group C2/c with a= 0.8078(5), b=2.6020(18), c=1.2191(7) nm, β= 99.38 (1)°, V= 2.528(3) nm3, and Z = 4. The structure comprises discrete cations [Co(mpt)2{P(OCH3)3}2.] and anions BF4- , in which the cobalt (Ⅲ) atom is coordinated to two chelate mpt- and two as-oriented monodentate P(OCH3)3 ligands in a highly distorted octahedral geometry. The most distorted angles are S(2)-Co(1)-S(2a) of 162.23(10)° and N(1)-Co(1)-S(2) of 71. 47 (13)°, the latter is caused by the geometric constraint of the bidentate ligand mpt- . Cyclic voltammetry has been used to study the electrochemical behavior of the title complex on the R electrode in MeCN solution with 0.1 mol·L-1 of Bun4NBF4 as electrolyte. The results indicate that the title complex is unstable in MeCN.  相似文献   

2.
The molecular structures of blue dichloro‐tetrakis(acrylamide) cobalt(II), [Co{O‐OC(NH2)CH=CH2}4Cl2] ( 1 ) and pink hexakis(acrylamide)cobalt(II) tetrachlorocobaltate(II), [Co{O‐OC‐(NH2)CH=CH2}6][CoCl4] ( 2 ), characterized by single X‐ray diffraction, IR spectroscopy and elemental analyses, are described. The coordination of CoII in 1 involves a tetragonally distorted octahedral structure with four O‐donor atoms of acrylamide in the equatorial positions and two chloride ions in the apical positions. The second complex 2 in ionic form contains CoII cations surrounded by an octahedral array of O‐coordinated acrylamide ligands, accompanied by a [CoCl4]2? anion.  相似文献   

3.
The heteroleptic neutral tri‐tert‐butoxysilanethiolate of cobalt(II) incorporating ammonia as additional ligand ( 1 ) has been prepared by the reaction of a cobalt(II) ammine complex with tri‐tert‐butoxysilanethiol in water. Complex 1 , dissolved in hexane, undergoes oxidation in an ammonia saturated atmosphere to the ionic cobalt(III) compound 2 . Molecular and crystal structures of 1 and 2 have been determined by single crystal X‐ray structural analysis. 1 forms a dimeric molecule [Co{μ‐SSi(OBut)3}{SSi(OBut)3}(NH3)]2 with a folded central Co2S2 ring and distorted tetrahedral ligand arrangement at both CoII atoms (CoNS3 core). The product 2 is composed of the octahedral CoIII complex cation [Co{SSi(OBut)3}2(NH3)4]+ and the tri‐tert‐butoxysilanethiolate anion. Within the crystal two pairs of ions interact by hydrogen bonds forming well separated entities. 1 and 2 are the first structurally characterized cobalt thiolates where metal is also bonded to ammonia and 2 is the first cobalt(III) silanethiolate.  相似文献   

4.
Solvatothermal syntheses have been exploited to effect the isolation of three novel polyoxoalkoxometalate clusters, [{Fe(OH)(CH3CN)2} Fe6OCl6{(OCH2)3CCH2OH}4] (1), [Fe10O2Cl8{(OCH2)3CCH2CH3}6] (2), and [(VO)2Fe8O2Cl6{(OCH2)3CCH2CH3}6] (3). The structure of 1 may be described as a hexametalate core {Fe6OCl6}10+, consisting of a octahedral arrangement of chloride ligands encasing an octahedron of six Fe(III) sites, with a central oxo group. The remaining four coordination sites at each octahedral iron center are occupied by doubly bridging oxygen donors from the trisalkoxo ligands. One triangular face of this substructure, defined by three oxygen atoms, from three adjacent trisalkoxo ligands, is capped by the {Fe(OH)(CH3CN)2}2+ subunit. The structure of 2 is based on the decametalate core of edge-sharing octahedra. The eight peripheral Fe(III) sites of the cluster bond to four oxygen donors from the trisalkoxo ligands, a terminal Cl ligand, and one of the 6-oxo groups. The two central iron sites are linked to four oxygen donors from the trisalkoxo ligands and to both of the 6-oxo groups. Cluster 3 is structurally related to 2 with two {FeCl}2+ units replaced by {VO}2+ groups.  相似文献   

5.
Two novel dinuclear Zn(II) and tetranuclear Co(II) complexes of a tetradentate N2O2 Schiff base ligand (H2 L = N,N′-bis-(4-hydroxysalicylidene)-1,3-diaminopropane) were prepared. The structures of the H2 L ligand, [4(Zn2 L (μ-O2CCH3)(O2CCH3)(H2O))]⋅4CH3OH⋅3H2O (complex 1 ) and [Co4 L 2(μ-O2CCH3)2(O2CCH3)2]⋅2H2O (complex 2 ) were unambiguously characterized by elemental analysis, mass spectrometry, Fourier-transform infrared spectroscopy (FT-IR), 1H nuclear magnetic resonance (NMR), and UV–Vis spectroscopy. Single crystal X-ray diffraction studies revealed that two Zn(II) nuclei of 1 were connected through μ-phenolato and μ-acetato bridges and had distorted square pyramidal and distorted octahedral coordination geometries. Four Co(II) nuclei of 2 , on the contrary, showed a Co4O4 cubane-like configuration in which Co(II) cations and O atoms were located at alternating corners of a distorted cube. Density functional theory studies at the B3LYP/6–31 G(d) level were carried out to gain an insight into the thermodynamic stability of the complexes. in vitro cytotoxicity of the ligand and the complexes were evaluated using the MTT assay against breast cancer MCF7 cells, melanoma cancer A375 cells, and prostate cancer PC3 cells as representative human cancer cell lines. Complex 1 showed a remarkable activity against A375 and PC3 cancer cell lines. In addition, 1 and 2 were used as precursors to produce zinc and cobalt oxide nanoparticles via pyrolysis technique. The resulting ZnO and Co3O4 nanoparticles were characterized using FT-IR spectroscopy, UV–Vis diffuse reflectance spectroscopy, powder X-ray diffraction, and field emission scanning electron microscopy. Then, these nanoparticles were used as heterogeneous catalysts in the oxidation of benzyl alcohol with hydrogen peroxide at room temperature. Both catalysts showed good recyclability with a negligible decrease in their efficiency during four catalytic cycles. The results of theoretical calculations showed that the most stable product was benzaldehyde, which is in good agreement with the obtained experimental results.  相似文献   

6.
7.
In the present study, the ?5-(4-dimethylaminobenzylidene)rhodanin-modified SBA-15? was applied as stable solid sorbent for the separation and preconcentration of trace amounts of cobalt ions in aqueous solution. SBA-15 was modified by ?5-(4-dimethylaminobenzylidene)rhodanin reagent. The sorption of Co2+ ions was done onto modified sorbent in the pH range of 6.8–7.9 and desorption occurred in 5.0 mL of 3.0 mol L?1 HNO3. The results exhibit a linear dynamic range from 0.01 to 6.0 mg L?1 for cobalt. Intra-day (repeatability) and inter-day (reproducibility) for 10 replicated determination of 0.06 mg L?1 of cobalt was ±1.82% and ?±1.97%?. Detection limit was 4.2 µg L?1 (3Sb, n = 5) and preconcentration factor was 80. The effects of the experimental parameters, including the sample pH, flow rates of sample and eluent solution, eluent type and interference ions were studied for the preconcentration of Co2+. The proposed method was applied for the determination of cobalt in standard samples, water samples and agricultural products.  相似文献   

8.
A new μ3-oxo trinuclear chromium(III) propionate cluster, [Cr33-O)(O2CCH2CH3)6(pyr)3]NO3·0.25(H2O) (1), has been synthesized by reaction of a μ3-oxo trinuclear chromium(III) propionate precursor [Cr33-O)(O2CCH2CH3)6(H2O)3]NO3 with a pyrazol ligand (pyr) and characterized by IR spectroscopy, single-crystal X-ray structure determination, and thermal analysis. Magnetic susceptibility and magnetization studies revealed antiferromagnetic exchange interactions within the trinuclear Cr(III) cluster (J = ?11.9 cm?1) and determined the electronic ground state (S = ½) of the compound.  相似文献   

9.
In acid-media ([H+] = 0.01–0.06 M), each of the thiol compounds, D-penicillamine (PEN, LPH2) and captopril (CAP, LCH2) exist in several proton-dependent forms which can reduce the superoxo complex [(en)(dien)CoIII(O2)CoIII(en)(dien)]5+ (1) to the corresponding peroxo [(en)(dien)CoIII(O2)CoIII(en)(dien)]4+ (2) or the hydroperoxo complex [(en)(dien)CoIII(OOH)CoIII(en)(dien)]5+ (3). The observed first-order rate constants, ko,P and ko,C for PEN and CAP increase with the increase in [TPEN] and [TCAP] (which are the analytical concentrations of the respective thiols) but decrease with the increase in the media-acidity ([H+]) and the media ionic strength (I). The protolytic equilibria in aqueous solution allow several potentially reducing forms to coexist for both PEN (LPH3+, LPH2, LPH?, and LP2?) and CAP (LCH2, LCH?, LC2?) but the kinetic analyses reveal that the order of reactivity for the species are LPH3+ ~ LPH2 <<< LPH? and LCH2 < LCH? <<< LC2?, respectively. The predominance and higher reactivities of the anionic species, LPH? and LC2? are supported by the negative slopes of the plots of ko,P or ko,C versus I. Moreover, a large value of kH/kD for PEN suggests an inner-sphere electroprotic reaction pathway while the absence of such effect for CAP strongly supports an outer-sphere electron transfer reaction. These propositions are supported by the structural features of LPH? and LC2?.  相似文献   

10.
Two new binuclear cobalt(II) complexes, [Co2 L1 (μ2‐DPP)]2+ ( 1 ) (H L1 = N, N, N′, N′‐ tetrakis (2‐benzimidazolylmethyl)‐2‐hydroxyl ‐1,3‐diaminopropane; DPP = diphenylphosphinate) and [Co2 L2 (μ2‐BNPP)2]+ ( 2 ) (H L2 = 2,6‐bis‐[N,N‐di(2‐ pyridylmethyl)aminomethyl]‐4‐methylphenol, BNPP = bis(4‐nitrophenyl)phosphate) have been synthesized and their crystal structures and magnetic properties are shown. In 1 , each CoII atom has a distorted trigonal bipyramidal coordination sphere with a N3O2 donor set and the central two CoII atoms are bridged by one alkoxo‐O atom and one μ2‐DPP ion with the Co1‐Co2 separation of 3.542Å. In 2 , each CoII atom has a pseudo octahedral environment with a N3O3 donor set and the central two CoII atoms are bridged by a phenolic oxygen atom of L2 and two μ2‐BNPP ions with the Co1‐Co2 separation of 3.667Å. Susceptibility data of 1 and 2 indicate intramolecular antiferromagnetic coupling of the high‐spin CoII atoms.  相似文献   

11.
Searching for prospective luminescent materials, the series of new lanthanide coordination compounds CsLnL4 (Ln = La, Pr, Nd, Sm – Er, and Yb; L? = {C6H5CONPO(OCH3)2}-) was synthesized. X-ray diffraction studies of CsNdL4 and CsYbL4 have been performed establishing polymeric structures of the tetrakis-complexes built from [LnL4]? anions and cesium cations functioning as linkers. The IR, absorption, emission, excitation spectra, and decay time measurements at 298 and 77 K, as well as thermal gravimetric analyses, were used to characterize the complexes.  相似文献   

12.
The reaction of Hppko (Hppko = phenyl 2‐pyridyl ketone oxime) and CoCl2 · 6H2O in the CH3OH solvent with the presence of triethylamine (NEt3) at room temperature and the exposure to air resulted in the formation of a new pentanuclear, mixed‐valence cobalt complex with the molecular formula [{CoII(CH3O)3}2{CoIII33‐O)(ppko)3}Cl2]. X‐ray single crystal analysis displays a trigonal bipyramid configuration with the terminal two CoII ions wrapping an triangle [CoIII3O]7+ core. The intermolecular C–H ··· O and C–H ··· Cl interactions form a 2D network framework. The analysis of magnetic susceptibility revealed the dominant antiferromagnetic interactions and strong orbital contribution of CoII ions.  相似文献   

13.
Two new cobalt(III) complexes of the hexadentate ligand [1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane] (H2bpctb) with N4S2 donor set atoms have been synthesized. A reaction of Co(CH3COO)2·4H2O with (H2bpctb) leads to the formation of [CoIII(bpctb)]PF6 (1) having a CoN2(pyridine)N′2(amide)S2(thioether) coordination by symmetric bpctb2? ligand. A similar reaction under slightly different conditions, however, gives [CoIII(L a )(L b )] (2), resulting from a C–S bond cleavage reaction triggered by an acetate ion as a base, having CoN2(pyridine)N′2(amide)S(thioether)S′(thiolate) coordination. These two Co(III) complexes have been characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structures of [CoIII(bpctb)]PF6 (1) in the form of the solvate (1·MeOH·H2O) and of [CoIII(L a )(L b )] (2) have been determined by X-ray crystallography. The Co atoms of both complexes exhibit distorted octahedral geometry. The electrochemical investigation of [Co(bpctb)]PF6·MeOH·H2O (1·MeOH·H2O) and [CoIII(L a )(L b )] (2) by cyclic voltammetry reveals a reversible CoIII–CoII redox process at E 1/2 = ?0.32 V (ΔE p = 80 mV); for 1, and E 1/2 = ?0. 87 V (ΔE p = 70 mV) for 2.  相似文献   

14.
Rhenium Complexes Stabilized by Tris-chelating Oxygen Ligands: Potential New Radiopharmaca? Ris-chelating oxygen ligands of the general formula L? = [(C5H4R)Co{P(O)R′R″}3]? (R = COOCH3, COOH and R′ = OCH3; R = H and R′ = O(CH2)5COOCH3, O(CH2)5COOH; R″ = OCH3) have been synthesized. These ligands L? and others of the same type have been used to prepare the rhenium oxo complexes [LReO3] and [LReOX2] (X = Cl, Br, I). In order to judge their use in radioimmunotherapy the corresponding complexes containing radioactive rhenium isotopes have also been synthesized. The rhenium(VII) as well as the diamagnetic rhenium(V) complexes are stable in air in the solid state as well as in organic solvents. They hydrolyze slowly in water to yield perrhenic acid. The X-ray structures of the sodium salt Na[(C5H4COOCH3)Co{P(O)(OCH3)2}3] and of the rhenium complex [LReOBr2] (R = H, R′ = R″ = OCH3) have been determined. The sodium salt crystallizes in trimeric units with the composition [(NaL)3 · 3 H2O]. Each sodium has a distorted octahedral oxygen coordination. In [LReOBr2] the ReO4Br2 octahedron is only slightly distorted.  相似文献   

15.
Single‐ and double‐sided functionalized hybrid organic–inorganic Anderson polyoxomolybdates with GaIII and FeIII positioned as central heteroatoms have been synthesized in a mild, two‐step synthesis in an aqueous medium. Compounds 1 – 4 were isolated as hydrated salts, [TBA]3[GaMo6O18(OH)3{(OCH2)3CCH2OH}]×12 H2O ( 1 ) (TBA=tetrabutylammonium), Na3[FeMo6O18{(OCH2)3CCH2OH}2]×11 H2O ( 2 ), [TMA]2[GaMo6O18(OH)3{(OCH2)3CNH3}]×7 H2O ( 3 ) (TMA=tetramethylammonium), and Na[TMA]2[FeMo6O18(OH)3{(OCH2)3CNH3}](OH)×6 H2O ( 4 ). All the compounds were characterized based on single‐crystal X‐ray diffraction (SXRD), FTIR, UV/Vis, thermogravimetric, ESI‐MS, NMR, and elemental analyses. Compound 1 was also crystallized with two smaller organic cations, giving [TMA]3[GaMo6O18(OH)3{(OCH2)3CCH2OH}]×n H2O ( 5 ) and [GDM]3[GaMo6O18(OH)3{(OCH2)3CCH2OH}]×n H2O ( 6 ) (GDM=guanidinium) and were characterized based on UV/Vis, NMR, FTIR, and elemental analyses. The use of these compounds as additives in macromolecular crystallography was investigated by examining their hydrolytic stability by using ESI‐MS in a pH range of 4 to 9. Sodium dodecyl sulfate‐polyacrylamide gel electrophoresis (SDS‐PAGE) analysis showed that BSA remains intact in a solution containing up to 100 equivalents of 1 or 4 over more than four days at 20 °C. Zeta potential measurements demonstrate that 1 – 4 induce charge inversions on the positively charged surface of BSA (1 mg mL?1) with concentrations starting as low as 1.29 mM for compounds 1 and 2 , which have the highest negative surface charge.  相似文献   

16.
Two new transition metal dicyanamide complexes [Co2(tppz)(dca)4]·CH3CN ( 1 ) [tppz=tetra(2‐pyridyl)pyrazine, dca=dicyanamide] and [Co(tptz)(dca)(H2O)](dca) ( 2 ) [tptz=2,4,6‐tri(2‐pyridyl)‐1,3,5‐triazine] were synthesized and characterized by single crystal X‐ray diffraction analysis. In 1 each cobalt(II) atom is coordinated to three dca anions and one tppz molecule to form a distorted octahedral geometry, the neigbour two cobalt(II) atoms are bridged by one tppz ligand to form a dimer, then the cobalt(II) atoms in each dimer are joined together to form a ladder chain structure. In 2 the coordination geometry around the central metal is also distorted octahedral, each cobalt(II) atom is coordinated by two dca anions, one tptz molecule and one water ligand to form a cationic part, and the cationic part is linked with the free dca anions via the electrostatic attraction to give an infinite chain structure. Magnetic susceptibility measurement in the range of 2–300 K indicates that there are antiferromagnetic couplings between adjacent metal ions in 1 (T>29 K, (=?9.78 K, C=4.92 cm3·K·mol?1) and ferromagnetic couplings in 2 (T>150 K, (=7.97 K, C=2.59 cm3·K·mol?1) respectively.  相似文献   

17.
New complexes of cobalt(III) with the tridentate and tetradentate Schiff base ligands: 3-methoxy-2-{(Z)[(2-hydroxyphenyl)imino]methyl}phenol (H2L1), 4-[(2-hydroxyphenyl)imino]-2-pentanone (H2L2); and 2-((E)-1-(2-((E)-1-(2-hydroxy-4,5-dimethylphenyl)ethylideneamino)ethylimino)ethyl)-4,5 dimethylphenol (H2L3), namely [CoIII(L1)(N-MeIm)3]PF6 (1), [CoIII(L1)(py)3]ClO4 (2), [Co(L1)(py)3][Co(L1)2] (3) and [CoIII(L2)(N-MeIm)3]PF6 (4) and [Co(L3)(N-MeIm)2]PF6 (5), were synthesized and characterized by physico-chemical and spectroscopic methods. The crystal structures of the complexes were determined by X-ray crystallography. In each of these complexes, the cobalt(III) centre has a slightly distorted octahedral environment, utilizing all available coordination centres of the ligands. The complexes were also screened for in vitro antibacterial activities against four human pathogenic bacteria, and their minimum inhibitory concentrations indicated good antibacterial activities.  相似文献   

18.
In the title compound, [{η5‐CpCo[P(O)(OMe)2]3}Nd(O2CCH3)2]2, with a centrosymmetric mol­ecule, each Nd atom has an eight‐coordination environment, surrounded by a tripodal {LOMe = CpCo[P(O)(OMe)2]3} and four bridging acetato ligands. The coordination geometry around each Nd centre is described as a distorted square‐antiprism and the two different types of acetato ligands have μ‐O:O′‐ and μ‐O,O′:O′‐acetato coordination modes. The Nd—O distances are in the range 2.378 (4)–2.594 (5) Å and the Nd?Nd distance is 3.9913 (6) Å.  相似文献   

19.
The adducts of bis(O,O′-dialkylmonoselenophosphato)cobalt(II) complexes, Co{O(Se)P(OR)2}2(L)4 (where R?=?n-Pr, i-Pr; L?=?C5H5N, NC5H4Me-2, NC5H4Me-3), were synthesized by in situ reactions of CoCl2?·?6H2O, Lewis base, and NaO(Se)P(OR)2. The single crystal structure of Co{O(Se)P(OiPr)2}2(C5H5N)4 shows distorted octahedral geometry around cobalt(II) and monoselenophosphates are trans. The CoN4 forms a square plane. These bis(O,O′-dialkylmonoselenophosphato)cobalt(II) adducts were characterized by elemental analyses, spectroscopic techniques (UV-Vis, infrared, 1H and 31P), and magnetic moment measurements.  相似文献   

20.
A new ladder structure of [(n-BuSn(O)O2CC6HF3OCH3)2-n-BuSn(O2CC6HF3OCH3)3]2 (1) has been synthesized and characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectra and X-ray crystallography. All the tin atoms are six-coordinate and display distorted octahedral geometry. A series of C–H ;··· ;F and π–π stacking interactions play an important function in the supramolecular aggregation.  相似文献   

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