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1.
TeX4 (X = Cl, Br) react in HCl/HBr with [Ph(CH3)2Te]X (X = Cl, Br) to give [PhTe(CH3)2]2[TeCl6] (1) and [PhTe(CH3)2]2[TeBr6] (2). The reaction of PhTeX3 (X = Cl, Br, I) in cooled methanol with [(Ph)3Te]X (X = Cl, Br, I) leads to [Ph3Te][PhTeCl4] (3), [Ph3Te][PhTeBr4] (4) and [Ph3Te][PhTeI4] (5). In the lattices of the telluronium tellurolate salts 1 and 2, octahedral TeCl6 and TeBr6 dianions are linked by telluronium cations through Te?Cl and Te?Br secondary bonds, attaining bidimensional (1) and three-dimensional (2) assemblies. The complexes 3, 4 and 5 show two kinds of Te?halogen secondary interactions: the anion-anion interactions, which form centrosymmetric dimers, and two identical sets of three telluronium-tellurolate interactions, which accomplish the centrosymmetric fundamental moiety of the supramolecular arrays of the three compounds, with the tellurium atoms attaining distorted octahedral geometries. Also phenyl C-H?halogen secondary interactions are structure forming forces in the crystalline structures of compounds 3, 4 and 5.  相似文献   

2.
Rhenium(I) tricarbonyl complexes with bispyridine ligands bearing sulfur-rich pendant, Re(CO)3(Medpydt)X (Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate; X = Cl, 1; X = Br, 2) and Re(CO)3(MebpyTTF)X (MebpyTTF = 4,5-bis(methyloxycabonyl)-4′,5′-(4′-methyl-2,2′-dipyrid-4-ylethylenedithio)-tetrathiafulvalene; X = Cl, 5; X = Br, 6), were prepared from the reactions between Re(CO)5X (X = Cl, Br) and Medpydt or MebpyTTF, respectively. Hydrolysis of the above complexes afforded the analogues with carboxylate derivatives, Re(CO)3(H2dpydt)X (X = Cl, 3; X = Br, 4) and Re(CO)3(H2bpyTTF)X (X = Cl, 7; X = Br, 8). The crystal structures for complexes 1 · 2H2O, 5 and 6 were determined using X-ray single crystal diffraction. UV-Vis absorption spectra of the rhenium complexes show the intraligand and MLCT transitions. Electrochemical behaviors of all new compounds were studied with cyclic voltammetry. Upon irradiation, complexes 3-6 exhibit blue to red emissions in fluid solutions at the room temperature. The performance of complexes 3, 4, 7 and 8 as photosensitizers for anatase TiO2 solar cells was preliminarily investigated as well.  相似文献   

3.
A series of five gold(I) halide complexes with the two isomeric methoxy-substituted triarylphosphines, tris(2-methoxyphenyl)phosphine [P(oanis)3], [AuP(oanis)3X] [for X = Cl, (1); X = Br, (2) and X = I, (3)] and tris(4-methoxyphenyl)phosphine [P(panis)3], [AuP(panis)3X] [for X = Br (4) and X = I (5)] have been synthesized and characterized by single crystal X-ray diffraction and solution 31P{1H} NMR spectroscopy. The structure determinations confirm the expected presence of linear two-coordination about the gold centres in all five complexes with bond distance and angle data typical of this type of compound [Au–P, 2.239(2)–2.259(3) Å; Au–Cl, 2.294(2) Å; Au–Br, 2.385(2)–2.402(2) Å; Au–I, 2.546(1)–2.554(1) Å; P–Au–X; 175.3(1)–180°]. All analogues except the iodo complex 5 crystallize with one complex molecule in the crystallographic asymmetric unit. The bromo and iodo complexes 2 and 3 constitute a trigonal isomorphous set while the bromo complex 4 is also isomorphous with the previously determined chloro complex [AuP(panis)3Cl]. The 2-methoxy analogues are stabilized by significant methoxy-O?Au interactions.  相似文献   

4.
We report a combined experimental and computational study of new rhenium tricarbonyl complexes based on the bidentate heterocyclic N-N ligands 2-(4-methylpyridin-2-yl)benzo[d]-X-azole (X = N-CH3, O, or S) and 2-(benzo[d]-X-azol-2-yl)-4-methylquinoline (X = N-CH3, O, or S). Two sets of complexes are reported. Chloro complexes, described by the general formula Re(CO)3[2-(4-methylpyridin-2-yl)benzo[d]-X-azole]Cl (X = N-CH3, 1; X = O, 2; X = S, 3) and Re(CO)3[2-(benzo[d]-X-azol-2-yl)-4-methylquinoline]Cl (X = N-CH3, 4; X = O, 5; X = S, 6) were synthesized heating at reflux Re(CO)5Cl with the appropriate N-N ligand in toluene. The corresponding pyridine set {Re(CO)3[2-(4-methylpyridin-2-yl)benzo-X-azole]py}PF6 (X = N-CH3, 7; X = O, 8; X = S, 9) and {Re(CO)3[2-(benzo[d]-X-azol-2-yl)-4-methylquinoline]py}PF6 (X = N-CH3, 10; X = O, 11; X = S, 12) was synthesized by halide abstraction with silver nitrate of 1-6 followed by heating in pyridine and isolated as their hexafluorophosphate salts. All complexes have been fully characterized by IR, NMR, electrochemical techniques and luminescence. The crystal structures of 1 and 7 were obtained by X-ray diffraction. DFT and time-dependent (TD) DFT calculations were carried out for investigating the effect of the organic ligand on the optical properties and electronic structure of the reported complexes.  相似文献   

5.
The reaction of mercury(II) halides with 1,2-bis(diphenylphosphino)ethane monoxide (dppeO) in 1:1 molar ratio yielded P,O-coordinated polymers having the empirical formula [HgX2(dppeO)]n [X = Cl (1), Br (2), I (3)]. In contrast, the reaction between the same reactants in a 1:2 molar ratio yielded the P, P-coordinated monomeric complexes, HgX2(dppeO)2[X = Cl (4), Br (5), I (6)]. The structures of 2, 3, 4 and 5 have been characterized crystallographically. The results indicate that the geometry around the mercury atom in each of these molecules is tetrahedral with considerable distortion. The 31P NMR spectra of the 1:1 complexes indicate the dissociation of the Hg–O bond in solution.  相似文献   

6.
The ligands (HL1, HL2 and HL3) have been prepared and their reaction with fac-[ReX(CO)3(CH3CN)2] (X = Br, Cl) in chloroform gave the adducts [ReX(CO)3(HL)] (1a X = Cl, R = H; 1a′ X = Br, R = H; 1b X = Cl, R = CH3; 1b′ X = Br, R = CH3; 1c X = Cl, R = Ph; 1c′ X = Br, R = Ph) in good yield. All the compounds have been characterized by elemental analysis, mass spectrometry (FAB), IR and 1H NMR spectroscopic methods, and the structures of the ligands have been elucidated by X-ray diffraction. In the case of HL1, we have tried the reaction with [ReX(CO)5] (X = Br, Cl) in toluene and we proved the formation of the adduct also by this way by the isolation of single crystals of 1a′ · ½C7H8.  相似文献   

7.
The reaction of Ni(OAc)2, NiX2 (X = Cl, Br) or CoCl2 with the proligand 2-amino-2-methyl-1,3-propanediol (ampdH2) affords a new family of tetranuclear complexes. The syntheses of [Ni4(OAc)4(ampdH)4] (1) and [M4X4(ampdH)4] (M = Ni, X = Cl, 2; M = Ni, X = Br, 3; M = Co, X = Cl, 4) are reported, together with the single crystal X-ray structures of 1, 2 and 4 and the magnetochemical characterization of 1, 3 and 4. Each member of this family of complexes displays a low symmetry structure that incorporates a {M4O4} core unit based on a distorted cubane. Magnetic measurements reveal ferromagnetic exchange interactions for 1, 3 and 4. These give rise to S = 4 ground state spins for the tetranuclear Ni complexes and an anisotropic effective S′ = 2 ground state for the Co complex.  相似文献   

8.
N-thioamide thiosemicarbazone derived from 4-(methylthio)benzaldehyde (R = H, HL1; R = Me, HL2 and R = Ph, HL3) have been prepared and their reaction with fac-[ReX(CO)3(CH3CN)2] (X = Br, Cl) in methanol gave the adducts [ReX(CO)3(HLn)] (1a X = Cl, n = 1; 1a′ X = Br, n = 1; 1b X = Cl, n = 2; 1b′ X = Br, n = 2; 1c X = Cl, n = 3; 1c′ X = Br, n = 3) in good yield.All the compounds have been characterized by elemental analysis, mass spectrometry (ESI), IR and 1H NMR spectroscopic methods. Moreover, the structures of HL2, HL3, HL3·(CH3)2SO and 1b′·H2O were also elucidated by X-ray diffraction. In 1b′, the rhenium atom is coordinated by the sulphur and the azomethine nitrogen atoms (κS,N3) forming a five-membered chelate ring, as well as three carbonyl and bromide ligands. The resulting coordination polyhedron can be described as a distorted octahedron.The structure of the dimers is based on rhenium(I) thiosemicarbazonates [Re2(L1)2(CO)6] (2a), [Re2(L2)2(CO)6] (2b) and [Re2(L3)2(CO)6] (2c) as determined by X-ray studies. Methods of synthesis were optimized to obtain amounts of these thiosemicarbazonate complexes. In these compounds the dimer structures are achieved by Re-S-Re bridges, where S is the thiolate sulphur from a κS,N3-bidentate thiosemicarbazonate ligand.Some single crystals isolated in the synthesis of 2b contain [Re(L4)(L2)(CO)3] (3b) where L4 (=2-methylamine-5-(para-methylsulfanephenyl)-1,3,4-thiadiazole) is originated in a cyclization process of the thiosemicarbazone. Furthermore, the rhenium atom is coordinate by the sulphur and the thioamidic nitrogen of the thiosemicarbazonate (κS,N2) affording a four-membered chelate ring.  相似文献   

9.
Copper(I) complexes of short-bite aminobis(phosphonite), PhN{P(–OC10H6(μ-S)C10H6O–)}2 (1) have been synthesized. Reactions of 1 with an excess of CuX (X = Cl, Br, and I) afforded the ligand-bridged binuclear complexes, [PhN(PR-κP)2{Cu(μ-X)(MeCN)}2] (2, X = Cl; 3, X = Br; 4, X = I; R = –OC10H6(μ-S)C10H6O–), whereas treatment with 0.5 equiv. of [Cu(MeCN)4]PF6 produces the mononuclear bischelated cationic complex, [{PhN(PR-κP)2}2Cu](PF6) (5). Single crystal X-ray structures of complexes 3 and 4 are reported. Complex 3 shows strong π–π stacking interactions between the naphthyl moieties, whereas complex 4 shows ligand-supported Cu?Cu metallophilic interactions.  相似文献   

10.
The synthesis and properties of heterobimetallic Ti-Cd complexes of type {[Ti](μ-η12-CCR)2}CdX2 ([Ti] = Ti(η5-C5H4SiMe3)2; R = SiMe3: 3a, X = Cl; 3b, X = Br; 3c, X = I; R = Fc: 3d, X = Br; Fc = Fe(η5-C5H4)(η5-C5H5) is reported. These compounds were accessible by treatment of [Ti](CCR)2 (1a, R = SiMe3; 1b, R = Fc) with the cadmium salts CdX2 (2a, X = Cl; 2b, X = Br; 2c, X = I) in a 1:1 M ratio in diethyl ether. Dissolving, for example, 3b in tetrahydrofuran afforded coordination polymer [Cd(μ-Br)2(thf)2]n (4) along with the tweezer molecule 1a. Treatment of 3b with two equiv of LiCCFc (5) gave {[Ti](μ-η12-CCSiMe3)2}Cd(CCFc)2 (6) which eliminated at ambient temperature the all-carbon buta-1,3-diyne FcCC-CCFc (7) producing 1a and elemental Cd. The same reaction behavior was observed, when 2b was reacted with 5. The thus obtained bis(alkynyl) cadmium complex Cd(CCFc)2 (8) is redox-active at low temperature producing 7 and Cd(0). When mercury halides HgX2 (9a, X = Cl; 9b, X = Br) are used, then the titanocene dihalides [Ti]X2 (10a, X = Cl; 10b, X = Br) together with Me3SiCC-CCSiMe3 (11) and Hg(0) were formed. Nevertheless, mercury acetylides were available by treatment of Hg(OAc)2 (12) with HCCFc (13) in a 1:2 M ratio. Thus obtained Hg(CCFc)2 (14) gave with [CuBr] (15) coordination polymer [{Hg(η2-CCFc)2}(Cu2(μ-Br)2]n (16), while with [AgPF6] oxidation of the ferrocenyl moieties took place affording dicationic [Hg(CCFc)2]2+ (18).The structures of 3b and 4 in the solid state are reported. Compound 3b shows the typical characteristics for heterobimetallic organometallic π-tweezer complexes with cadmium in a tetrahedral environment, while 4 corresponds to a one-dimensional coordination polymer in which the Cd(II) ions are linked in a edge-sharing fashion by bromide bridges in the pseudo-equatorial plane. The appropriate tetrahydrofuran molecules are completing the pseudo-octahedral coordination sphere at cadmium.The cyclic voltammogram of 14 is reported showing a single reversible redox event at E0 = 0.108 V with ΔEp = 76 mV indicating that there is no communication between the Fc termini along the mercury acetylide unit.  相似文献   

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