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1.
Reaction of L {L = [24]aneS 8, [28]aneS 8} with two molar equivalents of [Cu(NCMe) 4]X (X − = ClO 4−, BF 4−, PF 6−) in MeCN affords the white binuclear copper(I) complexes [Cu 2(L)] 2+. A single crystal X-ray structure determination of [CU 2([24]aneS 8)](BF 4) 2 shows two tetrahedral copper(I) centres, each of which is coordinated to four thioether sulphur-donors, Cu---S(1) = 2.263(3), Cu---S(4) = 2.363(3), Cu---S(7) = 2.349(3), Cu---S(10) = 2.261(3) Å. The Cu … Cu distance is 5.172(3) Å. A single crystal X-ray structure determination Of [CU 2([28]aneS 8)](ClO 4) 2 shows that this complex also contain two tetrahedral copper(I) centres, each coordinated to four thioether sulphur-donors, Cu---S(1) = 2.278(5), Cu---S(4) = 2.333(5), Cu---S(8) = 2.328(5), CU---S(11) = 2.268(5) Å. The Cu … Cu distance of 6.454(3) Å is greater than in [CU 2([24]aneS 8)] 2+ , reflecting the greater cavity size in [CU 2([28]aneS 8)] 2+. Cyclic voltammetry of [CU 2([24]aneS 8)] 2+ and [CU 2([28]aneS 8)] 2+ at platinum electrodes in MeCN (0.1 M nBU 4NPF 6) shows irreversible oxidations at Epa, = +0.88 V, +0.92 V vs Fc/Fc +, respectively, at a scan rate of 200 mV s −1. Coulometric measurements in MeCN confirm these oxidations to be two-electron (one electron per copper) processes to give binuclear copper(II) species. Oxidation of the binuclear copper(I) precursors with H 2SO 4 or HNO 3 affords ESR-active copper(II) species which presumably incorporate SO 42− and NO 3− bridges. 相似文献
2.
The reaction of [(CO)PPh 3) 2Re(μ-H) 2(μ-NCHPh)Ru(PPh 3) 2(PhCN)] (2) with HBF 4-Me 2O generates [(CO)PPh 3) 2Re(μ- H) 2(μ,η 1,η 2HNCHPh)Ru(PPh 3) 2(PhCN)][BF 4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh 3) 2 HRe(μ-H) 2(μ-NCHPh)Ru(PPh 3) 2(PhCN)][BF 4] (4). Attempted reduction of the imine ligand by a nucleophile (H − or CN −) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh 3) 2HRe(μ-H) 3Ru(PPh 3) 2(PhCN)][BF 4] (5) with liberation of benzyl amine. 相似文献
3.
The specific additions of one, three or four Ph 3PAu groups to [M(CO) 5] − (M=Mn, Re) are described. Thus [M(CO) 5] − in THF reacts with [(Ph 3PAu) 3O]BF 4 to give [(Ph 3PAu) 4Mn(CO) 4]BF 4. An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au 4Mn core with the Mn in an equatorial site. The previously known neutral (Ph 3PAu) 3M(CO) 4 clusters are formed by addition of two Ph 3PAu groups, using the mixed reagent [(Ph 3PAu) 3O]BF 4/[ppn][Co(CO) 4], to Ph 3PAuM(CO) 5, which itself is readily prepared from [M(CO) 5] − and Ph 3PAuCl. 相似文献
4.
The syntheses of the 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr i2; R′ = Me or Bu t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu t)(Me 3tach)(CH 2Ph) 2]. The tert-butylimido ligand in [Ti(NBu t)(Me 3tach)Cl 2] undergoes exchange with ArNH 2 (Ar = 4-C 6H 4Me or 2,6-C 6H 4Me or 2,6-C 6H 3Pr i2) to form the corresponding arylimides [Ti(NAr)(Me 3tach)Cl 2]. The Me 3tach ring in [Ti(NR)(Me 3tach)Cl 2] undergoes slow exchange with Bu t3tach or Me 3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu t3tach)Cl 2] and [Ti(NR)(Me 3tacn)Cl 2], respectively. The complexes [Ti(NR)(Me 3tach)X 2] (R = Bu t or 2,6-C 6H 3Pr i2; X = Cl or CH 2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me 3tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu t3tach)Cl 2] (R = Bu t or 2,6-C 6H 3Pr i2) and [Ti(NBu t)(Me 3tach)(X) 2] [X= Cl or CH 2Ph) are reported. Me 3tach and Bu t3tach = 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane, respectively. 相似文献
5.
Photodynamic properties of series of metal complexes having the general formula [M(diars) 2X 2]ClO 4 or BF 4 where M = Co 3+, Cr 3+, Rh 3+; X = Cl, Br, I, diars = o-phenylene bis(dimethylarsine) are studied. Photogeneration of singlet oxygen is monitored by both optical and EPR methods. In comparison with rose bengal ( ( 1O 2) for RB = 0.76), singlet oxygen generating efficiencies of these complexes are determined. Rate of N, N-dimethyl-4-nitrosoaniline (RNO) bleaching is found to be retarded by specific 1O 2 quencher NaN 3, confirming the involvement of 1O 2 as an active intermediate. Photolysis of these complexes in the presence of spin trap 5,5-dimethyl-1-pyrroline- N-oxide (DMPO) generates 12-line EPR spectra, characteristic of O 2− adduct. Photogeneration of O 2− is also monitored by optical spectroscopy using superoxide dismutase (SOD) inhibitable cytochrome c reduction assay. The results indicate that the [Co(diars) 2Br 2]ClO 4 complex possesses high ability to generate reactive oxygen species (ROS). Both Type I and II paths are involved in the photosensitisation of the metal complexes. The antimicrobial activity of the complexes against selected bacteria is estimated. The relationship between the enzymatic production of ROS and antimicrobial activity of the complexes is examined and a good correlation between two factors is found. The [CoBr 2(diars) 2]ClO 4 complex investigated in this study effect photo cleavage of the plasmid DNA (pUC18). 相似文献
6.
Reaction of [Pt 2(η 5-C 5Me 5) 2(η-Br) 3] 3+(Br −) 3 with C 5R 5H (R = H,Me) in the presence of AgBF 4 gives the first platinocenium dications, [Pt(η 5-C 5Me 5)(η 5-C 5R 5)] 2+(BF 4− ) 2. On electrochemical reduction, [pt(η 5-C 5Me 5) 2] 2+ yields [Pt(η 4-C 5Me 5H)(η 2-C 5Me 5)]+ BF 4−. kw]Cyclopentadienyl; Metallocenes; Platinum; Electrochemistry 相似文献
7.
Four novel tetranuclear macrocyclic complexes of the formula [(CuL i) 3Fe](ClO 4) 3·3H 2O ( i=1–4, L i are the dianions of the [14]N 4 and [15]N 4 macrocyclic oxamides, namely 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene, 2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene and 2,3-dioxo-5,6:14,15-dibenzo-7,13-bis(ethoxycarbonyl)-1,4,8,12-tetraazacyclotetradeca-7,12-diene] have been prepared and characterized. These complexes are the first examples of oxamido-bridged Cu(II)–Fe(III) heterometallic species. Cryomagnetic studies on [(CuL 1) 3Fe](ClO 4) 3·3H 2O (1) and [(CuL 3) 3Fe](ClO 4) 3·3H 2O (3) (77–300 K) revealed that the Cu(II) and Fe(III) ions interact antiferromagnetically through the oxamido bridge, with the exchange integral J=−30.8 cm −1 for 1 and J=−28.7 cm −1 for 3 based on
. The interaction parameters have been compared with that of the related [Cu 3Mn] compound. 相似文献
8.
The complexes [Ru(S,S) 2(PPh 3) 2] [S,S = EtCOCS 2−, (CH 2) 4NCS 2−] react with a variety of tertiary phosphines with the substitution of triphenylphosphine and the formation of [Ru(S,S) 2(PR 3) 2]. The reaction occurs with the formation ofthe cis isomer, except for the complex with PMe 2Ph that gives rise to the trans isomer as the crystal structure shows. The effect of the different phosphines on the ruthenium complex is analysed in terms of the spectroscopic and electrochemical properties of the isolated compounds. The cyclic voltammetric studies of the cis complexes show that isomerization to the trans isomer occurs on oxidation. This isomerization is not observed in the trans-[Ru(S,S) 2(PMe 2Ph) 2] complexes that give rise to stable trans-ruthenium(II)/ruthenium(III) couples. In a similar way the diphosphine complexes afford a quasi-reversible cis-ruthenium(II)/ruthenium(III) process. 相似文献
9.
Three novel uranyl complexes with organic phosphine oxide ligands and bridging fluorides have been synthesised and structurally characterised. In [ UO 2(μ-F)(TPPO) 3 2][BF 4] 2 · nC 6H 14, 1, and [ UO 2(-μF)(TBPO) 3 2][BF 4] 2 2, (where TPPO and TBPO are triphenylphosphine oxide and tri- n-butylphosphine oxide, respectively) two UO 2 2+ moieties are bridged by two fluorides with three additional terminal PO donor ligands coordinated to each uranium centre. The dicationic complexes are both charge balanced by two uncoordinated tetrafluoroborate anions. In the related structure, [UO 2(μ-F)(F)(DPPMO 2)] 2 · 2MeOH (3), terminal fluoride is also coordinated to both uranyl centres (where DPPMO 2 = bis(diphenylphosphine oxide)methane). All three complexes were prepared during attempted syntheses of complexes with tetrafluoroborate directly coordinated to uranium. It is clear from these results that the fluorophilicity of UO 2 2+ causes the abstraction of fluoride from [BF 4] −, with the weakly coordinating anion only present as a counter cation in 1 and 2, and absent completely in 3. 相似文献
10.
Complexes having the formula [C 5Me 5Fe(CO)-η 4-diene] + BF 4− have been prepared by reaction of [C 5Me 5Fe(CO) 2THF] +BF 4− with a range of dienes. A Brönsted plot derived from the rates of addition of amine nucleophiles suggests an essentially “soft” nature for the complexes diene. 相似文献
11.
Reactions among Cu(ClO 4) 2 · 6H 2O, Cu(acac) 2/VO(acac) 2 and 3-methoxysalicylaldehyde Picoloylhydrazone in different solvents give three complexes, [Cu 2L(acac)(H 2O) 2]ClO 4 (1), [Cu 4L 2(acac) 2(py) 2](ClO 4) 2 (2) and (VO 2) 2L 2Cu 2(acac) 2 (3) (acac = acetyl acetonate and py = pyridine). There is an extended 2D structure in complex 1 constructed by hydrogen bonds between the binuclear complex cation and the ClO 4− anion, and an extended 1D structure in complex 2 constructed by weak ππ stacking interactions between neighboring cyclic tetranuclear complex molecules. Complex 3 is the first oxovanadium–copper complex with a bridging oxo oxygen atom between the V atom and the Cu atom. The solid-state photoluminescent properties of the three title complexes have been studied. There is an antiferromagnetic interaction in 1. 相似文献
12.
The effect of γ radiation on 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4]) was investigated in detail. It was found that radiation induced an increase of UV absorption of the ionic liquid but no change in its glass transition point. Raman spectroscopy analysis indicates that the radiolysis of [bmim][BF 4] induces detectable destruction of alkyl-chain and scission of H-atoms of ring of imidizolium cation, and the relatively small changes of BF 4− anion. Viscosities of irradiated [bmim][BF 4] samples were measured at different shear rates and temperatures, and compared with irradiated [bmim][PF 6] samples. The plots of shear stress against shear rate indicates that [bmim][BF 4] is a Newtonian fluid, no matter with irradiation. The viscosity of irradiated [bmim][BF 4] decreased with increasing of temperature and followed an Arrhenius equation. However, radiation caused no change in the viscosity of [bmim][BF 4], but a decrease in the viscosity of [bmim][PF 6] by up to 10%. We conclude that the radiation stability of [bmim][BF 4] is higher than [bmim][PF 6]. 相似文献
13.
The nucleophile [ArTe −] generated in situ borohydride solution of Ar 2Te 2, reacts with 2-(chloromethyl) tetrahydrofuran and 2-(2-bromoethyl)-1,3-dioxolane resulting in L 1 and L 2, respectively. The complexes of palladium(II) and platinum(II) with L 1/L 2 having stoichiometries [MCl 2·L 2], [ML 2](ClO 4) 2, [(DPPE)ML 2](ClO) 4) 2, [(PPh 3) 2ML 2](ClO 4) 2 and [(phen)ML 2](ClO 4) 2 (where L = L 1/L 2 DPPE = Ph 2PC H 2CH 2PPh 2, PHEN = 1,10-phenanthroline and M = Pd/Pt) have been synthesized. IR, 1H, 125Te{ 1H} and 31P{ 1H} NMR and UV-vis spectral data of these species in conjunction with their molar conductance and molecular weight data have been used to authenticate the new species. In all complexes (1–20) the ligands L 1 and L 2 are coordinated through tellurium and in the complexes of formula [ML 2](ClO 4) 2 (M = Pd, Pt) the ligand is bidentate with the oxygen atom used in complexation. In solution, complexes PtCl 2L 2 exist as a mixture of cis and trans isomers whereas only the trans isomer was observed for the palladium analogues. The [(phen)PdL 2](ClO 4) 2(Q) quenches 1O 2 readily. The plot of log [Q] vs time is linear. Mechanism compatible with the experimental observations is proposed. 相似文献
14.
The nitrosyl complexes trans-[ReCl(NO)(dppe) 2]A 2 (1; A = BF 4 or NO 3; dppe = Ph 2PCH 2CH 2−PPh 2) and trans-[ReCl(NO)(dppe) 2][BF 4] (2) have been prepared from the reactions of NO[BF 4] or NO with trans-[ReCl(N 2)dppe) 2]. An unusual facile oxidation of NO to nitrate is involved in the formation of (1, A = NO 3), the X-ray structure of which is reported. 相似文献
15.
This work evaluates the operational stability of six different supported liquid membranes (SLMs) based on ionic liquids (ILs). [bmim +][PF 6−] , [bmim +][BF 4−] and [bmim +][NTf 2−] were used as supporting phase in Nylon ® and Mitex ® membranes. Scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX) analysis was used to characterize the membrane surface morphologically and examine the global chemical composition of the membranes and the distribution of the ILs within them. Study of the freshly impregnated membranes showed that, in all cases, the ILs were homogeneously distributed, mostly filling the pores of the membranes although, in some cases, a small amount of excess of IL was located on the external membrane surface. Stability tests were performed by keeping the respective impregnated membranes immersed for a week in a diffusion cell including two independent compartments and using n-hexane/n-hexane as the respective feed and receiving phases. The SEM–EDX study of membranes after continuous operation showed that the ILs were still retained within the membrane pores and only small losses of the IL initially located on the external surface were observed. These observations are in complete agreement with the ionic losses determined by mass balance. 相似文献
16.
The crystal structures of propionaldehyde complex ( RS, SR)-(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHCH 2CH 3)] + PF 6− (1b + PF 6s−; monoclinic, P2 1/ c (No. 14), a = 10.166 (1) Å, b = 18.316(1) Å, c = 14.872(2) Å, β = 100.51(1)°, Z = 4) and butyraldehyde complex ( RS, SR)-[(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHCH 2CH 2CH 3)] + PF 6− (1c +PF 6−; monoclinic, P2 1/ a (No. 14), a = 14.851(1) Å, b = 18.623(3) Å, c = 10.026(2) Å, β = 102.95(1)°, Z = 4) have been determined at 22°C and −125°C, respectively. These exhibit C
O bond lengths (1.35(1), 1.338(5) Å) that are intermediate between those of propionaldehyde (1.209(4) Å) and 1-propanol (1.41 Å). Other geometric features are analyzed. Reaction of [(η 5-C 5H 5)Re(NO)(PPh 3)(ClCH 2Cl)] + BF 4− and pivalaldehyde gives [(η 5-C 5H 5)Re(NO)(PPh 3)(η 2-O=CHC(CH 3) 3)] +BF 4− (81%), the spectroscopic properties of which establish a π C
O binding mode. 相似文献
17.
The nucleophilicity of the bridging atom of the selenium complex (μ-Se)[(η 5-C 5H 5)Fe(CO) 2] 2 (1) has been demonstrated by addition of the complex cation [(η 5-C 5H 5)Fe(CO) 2] +: Reaction of 1 with the ionic complex [(η 5-C 5H 5)Fe(CO) 2-(THF)][BF 4] cleanly yields the ionic trinuclear complex [(μ 3-Se)(η 5-C 5H 5)-Fe(CO) 23][BF 4] (3). This addition reaction converts the bridging selenium atom from a bent FeSeFe structure into a flattened Fe 3Se pyramid (X-ray diffraction studies), without significant changes in the iron-selenium bond lengths (244.9(<1) pm and 242.7(1)/243.3(1)/244.8(1) pm, respectively). These bonds are considered to be single bonds in accord with the EAN rule. 相似文献
18.
The successive reaction of chromium and tungsten hexacarbonyl, (CO) 6M (M = Cr, W), with [N=C(Ph)R] − and [Et 3O]BF 4 yields the alkylideneamino(ethoxy)carbene complexes (CO) 5M[C(OEt)N=C(Ph)R] (M = Cr (1), W (2); R = NMe 2 (a), tBu (b)). Ethoxide abstraction from 1 and 2 affords 2-azoniaallenylidene complexes, {(CO) 5M[CNC(Ph)R]} +BF 4− (3/4). The complexes 3 and 4 are best described as resonance hybrids of several limiting structures. On the basis of the spectroscopic data of the complexes 3a and 4a the limiting structure of an iminium-substituted isocyanide complex dominates. 相似文献
19.
Mononuclear copper(II) complexes of a family of pyridylmethylamide ligands HL, HL Me, HL Ph, HL Me3 and HL Ph3, [HL = N-(2-pyridylmethyl)acetamide; HL Me = N-(2-pyridylmethyl)propionamide; HL Ph = 2-phenyl- N-(2-pyridylmethyl)acetamide; HL Me3 = 2,2-dimethyl- N-(2-pyridylmethyl)propionamide; HL Ph3 = 2,2,2-triphenyl- N-(2-pyridylmethyl)acetamide], were synthesized and characterized. The reaction of copper(II) salts with the pyridylmethylamide ligands yields complexes [Cu(HL) 2(OTf) 2] (1), [Cu(HL Me) 2](ClO 4) 2 (2), [Cu(HL) 2Cl] 2[CuCl 4] (3), [Cu(HL Me3) 2(THF)](OTf) 2 (4), [Cu(HL Me3) 2(H 2O)](ClO 4) 2 (5a and 5b), [Cu(HL Ph3) 2(H 2O)](ClO 4) 2 (6), [Cu(HL)(2,2′-bipy)(H 2O)](ClO 4) 2 (7), and [Cu(HL Ph)(2,2′-bipy)(H 2O)](ClO 4) 2 (8). All complexes were fully characterized, and the X-ray structures vary from four-coordinate square-planar, to five-coordinate square-pyramidal or trigonal-bipyramidal. The neutral ligands coordinate via the pyridyl N atom and carbonyl O atom in a bidentate fashion. The spectroscopic properties are typical of mononuclear copper(II) species with similar ligand sets, and are consistent their X-ray structures. 相似文献
20.
Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO) 5− CrCNEt 2]BF 4 (I), reacts with PPh 3 with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh 3(CO) 4CrCNEt 2]BF 4 (III). Substitution of CO by PPh 3 in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO) 4CrCNEt 2 (IVa: X = Br, IVb: X = I), leads in a reversible reaction to the corresponding tricarbonyl complexes, mer-X(PPh 3)(CO) 3− CrNEt 2 (V), PPh 3 occupying the cis-position to the carbyne ligand. With PPh 3 in large excess both reactions follow a first-order rate law. This as well as the activation parameters (Δ H≠ = 104–113 kJ mol −1, Δ S≠ = 64–71 J mol −1 K −1) indicate a dissociative mechanism. 相似文献
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