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1.
Molecular iodine is oxidised by phosphorus pentafluoride in iodine pentafluoride at room temperature giving I2+, PF6?, and PF3. I2+ is formed from uranium hexafluoride under similar conditions, but further oxidation occurs depending on the reaction stoicheiometry used. In all cases uranium pentafluoride is formed. Copper(II) fluoride reacts with UF5 in acetonitrile at room temperature to give copper(II) hexafluorouranate(V), which is reduced by copper metal to give the copper(I) salt. The latter compound is formed from UF6 and Cu metal, via the CuII salt, only if a fresh Cu surface is used for the reduction step.  相似文献   

2.
Thermal studies have shown that metal(II) hexafluoro-arsenates of the types MF2·2AsF5 ( M = Mg, Ca, Sr, Mn, Co, Ni, Cd, Hg, Pb), 2MF2·3AsF5 (M = Fe, Cu, Zn) and MF2·AsF5 (M = Ag, Sn), prepared by the reaction of metal difluorides with AsF5 in anhydrous HF at room temperature, decompose when heated in an argon atmosphere. In all cases AsF5 is given off. For some of the adducts the decompositions proceed in one or more steps to give the original difluorides, but for others, the decompositions overlap one another. The greatest range of intermediate stoicheiometries results from the decompositions of the MF2·2AsF5 type adducts in which the metal difluoride content is a minimum. In decompositions of adducts of this type as many as three different intermediates, 2MF2·3AsF5, MF2·AsF5 and 2MF2·AsF5, may be observed.  相似文献   

3.
Tin(II) fluoride reacts with Lewis acids, AsF5 and SbF5, in a 2:1 ratio, to give salts of the [Sn2F3+] cation. Reaction of SnF·MF6 with SnF2 in liquid SO2 also produces the [Sn2F3] [MF6] salt. Tin-119 Mössbauer data are presented and compared with those for SnF2, SnF·MF6 and Sn(SbF6)2.  相似文献   

4.
The preparation and crystal structures of (4,11‐di­benzyl‐1,4,8,11‐tetra­aza­bi­cyclo­[6.6.2]­hexa­decane‐κ4N)copper(I) hexa‐fluorophosphate, [Cu(C26H38N4)]PF6, and acetonitrile(4,11‐dibenzyl‐1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐κ4N)‐copper(II) bis(hexafluorophosphate), [Cu(C2H3N)(C26H38‐N4)](PF6)2, are described. The CuI ion is tetracoordinated in a very distorted tetrahedron, while the CuII analogue is pentacoordinated in a square pyramid.  相似文献   

5.
The reaction of Cu(ClO4)2·6H2O, NaAsF6 and excess pyrazole yields hexakis­(pyrazole‐κN2)copper(II) bis­(hexa­fluoroarsenate), [Cu(C3H4N2)6](AsF6)2 or [Cu(pzH)6](AsF6)2 (pzH is pyrazole), (I). The analogous hexakis­(pyrazole‐κN2)copper(II) hexafluorophosphate perchlorate complex, [Cu(C3H4N2)6](PF6)1.29(ClO4)0.71 or [Cu(pzH)6](PF6)1.29(ClO4)0.71, (II), is obtained in a similar fashion, using KPF6 in place of NaAsF6. Both compounds contain the hitherto unknown [Cu(pzH)6]2+ complex cation, in which the copper(II) ion lies at the center of a regular octahedron of coordinated N atoms. The cation has crystallographically imposed symmetry. The X‐ray data indicate that the lack of the expected distortion can be accounted for by the presence of either static Jahn–Teller disorder or dynamic Jahn–Teller distortion.  相似文献   

6.
The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected CuI, AgI and AuI species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)4]BF4, compound 1 [Cu2(bqmpp)2](BF4)2 is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). CuI complex 2 [Cu4Cl3(bqmpp)2]BF4 contains a rarely observed Cu4Cl3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF6] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by 31P{1H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline-2-ylmethyl)bisphenyl-phosphine ( tqmbp ) compound [Ag2(tqmbp)2](SbF6)2 4 is formed by elimination of quinaldine. The Au(I) compound [Au2(bqmpp)2]PF6 ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around AuI.  相似文献   

7.
The reaction of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine (TMG2PA) ( 1 ) with CuI in MeCN results in the formation of [CuII(TMG2PAamid)I] ( 2 ) indicatingthat CuI is the target of an oxidative attack of the N‐H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)4][PF6] is used as the CuI source, [CuI2(TMGbenz)2][PF6]2 ( 3 ) is obtained instead. The use of the non‐coordinating counterion [PF6] apparently prevents CuI from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole‐guanidine ligand.  相似文献   

8.
A dinuclear copper(II) compound, [Cu(btssb)(H2O)]2 · 4(H2O) (1), and a 1-D chain copper(II) compound, [Cu(ctssb)(H2O)] n (2) [where H2btssb is 2-[(5-bromo-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid and H2ctssb is 2-[(3,5-dichloro-2-hydroxy-benzylidene)-amino]-ethanesulfonic acid], were prepared and characterized. Compound 1 crystallizes in the monoclinic space group P21/c, with a = 10.109(2) Å, b = 20.473(4) Å, c = 6.803(1) Å, β = 100.32(3)°, V = 1385.1(5) Å3, and Z = 2; R 1 for 1796 observed reflections [I > 2σ(I)] was 0.0357. The geometry around each copper(II) can be described as slightly distorted square pyramidal. The CuII ··· CuII distance is 5.471(1) Å. Compound 1 formed a 1-D network through O–H ··· O hydrogen bonds and 1-D water chains exist. The 1-D chain complex 2 crystallizes in the triclinic space group P 1, with a = 5.030(2) Å, b = 7.725(2) Å, c = 17.011(5) Å, α = 92.706(4)°, β = 97.131(4)°, γ = 102.452(3)°, V = 638.6(3) Å3, and Z = 2; R 1 for 1897 observed reflections [I > 2σ(I)] was 0.0171. In 2, Cu(II) was also a slightly distorted square pyramid formed by two oxygens and one nitrogen from ctssb, one oxygen from another ctssb, and one water molecule. The complex formed a 1-D chain through O–S–O bridge of ctssb ligand. The 1-D chain further constructed a double chain through O?H ··· O hydrogen bonds.  相似文献   

9.
Two new salts of the cation [CuI(dmp)2]+ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C14H12N2), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ2N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C14H12N2)2]2(PF6)2·0.5C12H10N4·C2H3N or [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C12H10N4], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ2N,N′)copper(I) dicyanamide, [Cu(C14H12N2)2](C2N3) or [Cu(dmp)2][N(CN)2], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.  相似文献   

10.
Mixed‐valence copper(I/II) atoms have been introduced successfully into a Pb/I skeleton to obtain two heterometallic iodoplumbates, namely poly[bis(tetra‐n‐butylammonium) [bis(μ3‐dimethyldithiocarbamato)dodeca‐μ3‐iodido‐hexa‐μ2‐iodido‐tetracopper(I)copper(II)hexalead(II)]], {(C16H36N)2[Cu4ICuIIPb6(C3H6NS2)2I18]}n , (I), and poly[[μ3‐iodido‐tri‐μ2‐iodido‐iodido[bis(1,10‐phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[CuICuIIPbI5(C12H8N2)2]·0.5I2}n , (II), under solution and solvothermal conditions, respectively. Compound (I) contains two‐dimensional anionic layers, which are built upon the linkages of CuII(S2CNMe2)2 units and one‐dimensional anionic Pb/I/CuI chains. Tetra‐n‐butylammonium cations are located between the anionic layers and connected to them via C—H…I hydrogen‐bonding interactions. Compound (II) exhibits a one‐dimensional neutral structure, which is composed of [PbI5] square pyramids, [CuII4] tetrahedra and [CuIIN4I] trigonal bipyramids. Face‐to‐face aromatic π–π stacking interactions between adjacent 1,10‐phenanthroline ligands stabilize the structure and assemble compound (II) into a three‐dimensional supramolecular structure. I2 molecules lie in the voids of the structure.  相似文献   

11.
Ag/CuI Mixed Occupancy in the Crystal Structures of the Copper(II) Cyanoargentates Cu(NH3)(py)Ag3?xCux(CN)5 · py From pyridine and ammonia containing CuII solutions, to which K[Ag(CN)2] and in part KCu(CN)2/KCN has been added, we obtained single crystals of mixed-valent copper compounds of variable composition Cu(NH3)-(py)Ag3-xCux(CN)5 · py. The phases corresponding to x = 0.39(1) ( I ) and to x = 1.243(6) ( II ) were characterized by X-ray structure analysis. They are isomorphous and crystallize with Z = 4 in the monoclinic space group P21/c. The lattice constants for I [and II , resp.] are: a = 923.8(2) [901.4(2)], b = 1226.8(2) [1227.3(2)], c = 1809.8(4) [1783.5(2)] pm, β = 91.41(3) [91.02(1)]°. The CuII cation shows trigonal bipyramidal [CuN5] coordination, with the neutral ligands in axial positions (mean value Cu? N for II : 201 pm), three N atoms of cyano bridges in equatorial ones (Cu? N: 206 pm). One of these bridges stems from a trigonal unit [AgCN(NC)2], the central atom of which is substituted by CuI to an extent of 39% in I , and completely in II . The two other bridges originate from two [Ag(CN)2]? groups, of which the more bent one may be partially occupied by CuI as well (24% in II ). The units mentioned are connected into meshes of elongated hexagons and further into puckered layers within the (010) plane, interpenetrating each other in pairs. A threedimensional linking of layers occurs by the trigonal Ag/CuI species forming centrosymmetric dimers, in which the metal coordination is completed to tetrahedral by a C-atom of the corresponding neighbouring group and short metal-metal distances of 279.1(3) pm in I and 264.1(1) pm in II appear. Details and relations are discussed.  相似文献   

12.
Syntheses and Crystal Structures of Cu and Ag Complexes with [Ta6S17]4— Ions as Ligands In the presence of phosphines saturated solutions of the thiotantalates (NEt4)4[(Ta6S17)] · 3MeCN react with copper or silver salts to give new heterobimetallic Ta—M—S clusters (M = Ag, Cu). These clusters contain the intact cluster core of the [Ta6S17]4— anion. Compounds [Cu(PMe3)4]3[(Ta6S17)Cu(PMe3)] · 2MeCN ( 1 ), (NEt4)[(Ta6S17)Ag3(PMe2iPr)6] · 5MeCN ( 2 ), [(Ta6S17)Cu4 (PMe2iPr)8] · MeCN ( 3 ), [(Ta6S17)Cu5Cl(PMe2iPr)9] · MeCN ( 4 ) and [Ta2Cu2S4Cl2(PMe2iPr)6] · 2MeCN ( 5 ) are presented herein. The structures of these compounds were elucidated by single crystal X‐ray structural analyses.  相似文献   

13.
Copper(I), copper(II), and thallium(III) hexafluoromolybdates(V), prepared by the oxidation of the metals in acetonitrile with molybdenum hexafluoride (A. Prescott, D.W.A.Sharp, and J.M. Winfield, J. Chem. Soc., Dalton Trans., 1975, 963) have been investigated by cyclic voltametry. Half wave potentials, E12 V vs. Agp+/Ag were obtained using a evacuable cell equipped with anexternal Agp+/Ag electrode, enabling strict anerobic conditions to be maintained. A number of reversible or quasi-reversible electron transfer processes have been observed, enabling comparison with synthetic work to be made. Results for CuI and CuII hexafluoromolybdates(V) are in accord with preparative experience. MoF6. MoVI/MoVE12 +1.600V, oxidises Cu metal to CuII in MeCN, and CuII is reduced by CuO to CuI , CulI/CuIE12 = +0.750 or +0.710V for CuI and CuII solutes respectively, CuI/CuOE12 = ?0.720V not reversible. A wave at E12 = ?0.350V is assigned to MoV/MoIV by analogy with AgI hexafluoromolybdate (D.W.A. Sharp, unpublished work). E12 data for I2 in MeCN, I2/I3- = 0.280, I3?/I? = -0.116V, suggest that reduction of MoF6? by I is not likely, in contrast to the situation in SO2 (A.J. Edwards and R.D. Peacock, Chem. Ind., 1960, 1441). Reduction of MoF6? by Cuo in MeCN should be feasible, but appears to be very slow. Pure TλIII hexafluoromolybdate(V) is obtained from Tλo and MoF6 only when the mole ratio MoF6:Tλ>5:1. Smaller ratios produce yellow solids in which Mo:Tλ is ca. 2:1. TλIII is a stronger oxidising agent than CuII in MeCN, as oxidation of CuI by TλIII is rapid and quantitative. However a reversible electron transfer wave assignable to TλIII/TλI is not observed in the expected fange +1.600 to +0.710V possibly because of solute-electrode interactions.  相似文献   

14.
A new copper(II) complex of an unsymmetrical tripodal ligand (NN2O222) derived from tris(2-aminoethylamine)amine (tren) by substitution of one aminoethyl group by an hydroxyethyl group has been synthesized and characterized by X-ray crystallographic methods as [(NN2O222)Cu(ImH)](ClO4)2·0.5H2O (NN2O222?=?2-[bis(2-aminoethyl)amino]ethanol; ImH?=?imidazole). Crystals of the complex are orthorhombic, space group Pna21, with a?=?29.983(10), b?=?15.568(5), c?=?8.127(3)?Å. Two similar monometallic cations exist in the asymmetric unit and in each case the Cu(II) ion is five-coordinate with tetragonally distorted trigonal bipyramidal geometry. Variable-temperature magnetic measurements show that there is very weak antiferromagnetic interaction between the metal ions. Cyclic voltammetry indicates quasi-reversible CuII/CuI redox behavior at +44?mV vs SCE. An antimicrobial activity study found that the complex is active against Candida albican, Staphylococcus aureus, Bacillus pumilus, Klebosiella pneumoniae and Escherichia coli, but to no greater extent than Cu(ClO4)2·6H2O.  相似文献   

15.
Reactions of carbonate radical (Co3 ) generated by photolysis or by radiolysis of a carbonate solution, with Cu(II) complexes of aminopolycarboxylic acids viz., Cu(II)ethylenediamine tetraacetate [CuIIEDTA]2− and Cu(II)-iminodiacetate [CuIIIDA] were studied at pH 10. 5 and ionic strength 0.2 mol·dm−3. Time-resolved spectroscopy and kinetics for the transients were studied using flash photolysis and stable products arising from the ligand degradation of the complex were ascertained by steady-state radiolysis experiments. From the kinetic data it is observed that CO3 , radical reacts initially with CuII-complex to form a transient intermediate having maximum absorption at 335 nm and 430 nm. From the subsequent reactions of this intermediate it was assigned to be CuIII. species. This Cu(III) species undergoes intermolecular electron transfer with the CuII-complex to give a radical intermediate which again slowly reacts with CuII-complex to give a long lived species containing Cu−C bond. This long lived species, however, slowly decomposed to give glyoxalic reaction between CuIII-complex and a suitable donor, the one electron reduction potential for [CuIIIEDTA]1−/[CuIIEDTA]2− and [CuIIIIDA]+1/CuIIIDA was determined.  相似文献   

16.
Summary Condensations of Cu(L-ser)2 and Cu(L-thr)2 (where L-ser=L-serinato anion and L-thr=L-threoninato anion) with formaldehyde at pH 4.5 yield two new optically active products:bis[L-(oxazolidine-4-carboxylato)]-copper(II) monohydrate (1) andbis[L-(N-hydroxymethyl-5-methyloxazolidine-4-carboxylato)]copper(II) dihydrate (2), respectively. Cu(D-ser)2 and Cu(D-thr)2 also undergo similar reactions. The new products are different from the products obtained from Cu(DL-ser)2 and Cu(DL-thr)2, and a mechanism has been suggested to explain the stereospecificity of these conversions. Condensation of Cu(L-ser)2 with formaldehyde and ammonia at pH 4.5 yields the new product, [3N,7N-(1,3,5,7-tetraazabicyclo-[3.3.1]nonyl)di(hydroxymethyl)-acetato]copper(II), (3). The compexes have been characterized by analytical and by i.r. electronic and c.d. spectral data. Complexes (1) and (2) undergo a reversible CuII/CuI redox process in aqueous media at –0.18 Vversus s.c.e.; complex (3) exhibits irreversible CuII/CuI reduction at –0.49 V confirming the presence of a rigid pentamethylenediaza-bridged ligand system.  相似文献   

17.
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N4Me2) ligand, yielding complexes of the general formula [(L‐N4Me2)Ru(µ‐tape)M(L‐N4Me2)](ClO4)2(PF6)2 with M = Fe {[ 2 ](ClO4)2(PF6)2}, Co {[ 3 ](ClO4)2(PF6)2}, and Ni {[ 4 ](ClO4)2(PF6)2}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)2Ru(μ‐tape)PdCl2](PF6)2 {[ 5 ](PF6)2} and [(dmbpy)2Ru(μ‐tape)PtCl2](PF6)2 {[ 6 ](PF6)2}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]4+ and [ 4 ]4+ were discussed on the basis of the X‐ray structures of [ 2 ](ClO4)4 · MeCN and [ 4 ](ClO4)4 · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand.  相似文献   

18.
The tridentate ligand 2-Oximino-3-thiosemicarbazone-2,3-butanedione (Hotsb) reacts with MCl2 (M = Ni2+ or Cu2+) to give rise to the mononuclear complexes [Ni(Hotsb)2]Cl2 · H2O (1) and [Cu(Hotsb)Cl2] · H2O (2). These complexes have been characterized by X-ray crystallography, spectroscopy, and cyclic voltammetry. The nickel(II) ion in (1) is in a six-coordinate octahedral environment being bonded to the two protonated tridentate ligands which occupy mer positions. The copper(II) ion in (2) is in a five-coordinate square-pyramidal geometry, in which the basal plane is made up the two nitrogens, sulfur, and chloride atom, while the other chloride atom is coordinated at the axial position. The cyclic voltammogram of the complexes displays two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic as well as infrared spectral properties of the title complexes are reported and discussed.  相似文献   

19.
New hybrid ligands are reported that combine two types of popular donor groups within a single linear scaffold, viz., a central pyrazolate bridge and two appended bis(N‐heterocyclic carbene) units; the ligand strands thus provide two potentially tridentate {NCC} compartments. The pyrazole/tetraimidazolium proligands, [H5L1](PF6)4 and [H5L2](PF6)4 , were synthesized via multi‐step protocols, and the NH prototropy of [H5L1](PF6)4 was examined by variable temperature (VT) NMR spectroscopy, giving solvent dependent activation parameters (ΔH? = 27.6 kJ · mol–1, ΔS? = –125 J · mol–1 · K–1 in [D3]MeCN; ΔH? = 40.4 kJ · mol–1, ΔS? = –86.9 J · mol–1 · K–1 in [D6]DMSO) that are in the range typical for pyrazoles. Reaction of the proligands with Ag2O gave hexametallic complexes [Ag6(L1)2](PF6)4 and [Ag6(L2)2](PF6)4 that involve all six potential donor atoms of the ligands, viz. the four CNHC and two Npz donors, in metal coordination. X‐ray crystallography revealed a chair‐like central {Ag6} deck in both complexes but different arrangements of the ligand strands, which goes along with significantly different AgI ··· AgI distances that indicate more pronounced argentophilic interactions in case of [Ag6(L1)2]4 +.  相似文献   

20.
《Polyhedron》2001,20(9-10):1079-1087
The crystal and molecular structure of sodium 5-sulfosalicylate dihydrate, Na[(H2Ssal)(H2O)2], (1) (H3Ssal=5-sulfosalicylic acid) has been determined through X-ray diffraction analysis. The 5-sulfosalicylate anion has lost the proton at the SO3H group but retains the usual intermolecular hydrogen bond between phenolic and carboxylic oxygen. The reaction in water of 1 with [Cu(II)(H2O)4]SO4·H2O, gives rise to the green sodium[triaqua(5-sulfosalicylato)copper(II)] 2 hemihydrate, Na[(H2O)3(Ssal)Cu(II)]·2×0.5H2O, (2). The 5-sulfosalicylate anion, (Ssal3−), coordinates rather unusually in the synsyn coordination mode since it binds bidentately the Cu(II) ion through the carboxylic and the phenolic oxygens, with Cu(II)Ocarboxylic=1.909(4) Å and Cu(II)Ophenolic=1.885(4) Å distances. Copper(II) completes its square-planar coordination with two water molecules and in addition, perpendicularly to the square-planar coordination plane, another two water molecules with long bonds are present (Cu(II)O=2.518 and 2.912 Å). The green complex 2 reacts easily with adenine in water at pH 7 giving rise to the violet tetraadeninato(diaqua)-bis(copper(II)) dihydrate, [Cu2(Ade)4(H2O)2])]·2H2O, (3) (Ade=adeninato monoanion). This complex, that geometrically resembles copper(II) acetate monohydrate, was already described by Sletten. Finally, on the basis of the present results a possible mechanism for the anticancer activity of complex 2 and of other Cu(II)–salicylate complexes is proposed and discussed.  相似文献   

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