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1.
Horst Kunkely 《Inorganica chimica acta》2006,359(1):388-390
The complexes AgI(tripod)X with tripod = 1,1,1-tris(diphenylphosphinomethyl)ethane and X− = Cl− and I− are luminescent in solution at r.t. It is suggested that the emission is a phosphorescence which originates from a tripod intraligand state for X = Cl (λmax = 464 nm) and a X− → tripod ligand-to-ligand charge transfer state for X = I (λmax = 482 nm). 相似文献
2.
Half sandwich complexes of the type [CpM(CO)nX] {X = Cl, Br, I; If, M = Fe, Ru; n = 2 and if M = Mo; n = 3} and [CpNiPPh3X] {X = Cl, Br, I} have been synthesized and their second order molecular nonlinearity (β) measured at 1064 nm in CHCl3 by the hyper-Rayleigh scattering technique. Iron complexes consistently display larger β values than ruthenium complexes while nickel complexes have marginally larger β values than iron complexes. In the presence of an acceptor ligand such as CO or PPh3, the role of the halogen atom is that of a π donor. The better overlap of Cl orbitals with Fe and Ni metal centres make Cl a better π donor than Br or I in the respective complexes. Consequently, M-π interaction is stronger in Fe/Ni-Cl complexes. The value of β decreases as one goes down the halogen group. For the complexes of 4d metal ions where the metal-ligand distance is larger, the influence of π orbital overlap appears to be less important, resulting in moderate changes in β as a function of halogen substitution. 相似文献
3.
Effendy Corrado di Nicola Adriano Pizzabiocca Neil Somers 《Inorganica chimica acta》2006,359(1):64-80
Single crystal X-ray structural characterizations are recorded for a number of adducts of MX:dpex (2:3) stoichiometry (MX = simple univalent copper or silver salt; dpex = Ph2E(CH2)xEPh2 (E = P, As)). CuX:dppe (2:3) (X = Cl, Br, I, CN) are binuclear [(dppe-P,P′)CuX(P-dppe-P′)CuX(P,P′-dppe)], all centrosymmetric. AgX:dpex (2:3) (dpex = ‘dpae’ (Ph2As(CH2)2AsPh2), X = Br, F3CCO2 (= ‘tfa’), F3CSO3 (≡ ‘tfs’); dpex = ‘dpape’ (Ph2As(CH2)2PPh2), X = CN, SCN, OClO3) are one-dimensional polymers ?-E′)1AgX(E-dpex-E′)2-AgX(E-dpex-E′)1AgX?, P, As sites scrambled in the latter. AgNO3:dpam (2:3) is also a one-dimensional polymer, ?AgO·NO·OAg(As-dpam-As)AgO·NO·OAg? (‘dpam’ ≡ Ph2As(CH2)2AsPh2). AgX:dpae (2:3) (X = I, CN, ClO4, NO3) and AgX:dpape (2:3) (X = Br, I, NO3) are two-dimensional polymers with large 30-membered macrocyclic rings; similar webs are found for dppx ligands in AgOH:dppb (2:3) and AgNCO, Agtfa:dpph (2:3) with 42- and 54-membered rings. Complexes AgX:dpape (1:3) (X = Cl, Br) are defined as mono-nuclear [XAg(Ph2P(CH2)2AsPh2)3] arrays, the unidentate ligands predominantly P-bound. Synthetic procedures for the adducts are reported, selected compounds being characterized both in solution (1H, 31P NMR, ESI MS) and in the solid state (IR). 相似文献
4.
Kimberly Edwards Alexander R. Parent Kelley C. Shortsleeves Louise N. Dawe 《Inorganica chimica acta》2011,368(1):141-151
The reactions of metal(II) chlorides and bromides with 8-methylquinoline (8-mequin) in neutral and acidic solutions were investigated. The reaction with ZnCl2, ZnBr2, CoCl2, CoBr2, CuCl2 or CuBr2 with the appropriate HX in water or aqueous ethanol gave complexes of the formula (8-mequin)2MX4 (1, M = Cu, X = Cl; 2, M = Cu, X = Br; 3, M = Co, X = Cl; 4, M = Co, X = Br) or (8-mequin)2ZnX4·nH2O (5, X = Cl, n = 0; 6, X = Br, n = 0; 7, X = Cl, n = 1; 8, X = Br, n = 1). Crystals of 1, 2 and 4-8 suitable for single crystal X-ray diffraction were obtained and the structures reported. Compounds 1 and 2 crystallize in the monoclinic space group C2/c, while 4-8 crystallize in the triclinic space group, . Variable temperature magnetic susceptibility data indicate very weak interactions for the copper compounds 1 and 2, while the magnetic behavior of 3 and 4 is dominated by single ion anisotropy, with weaker antiferromagnetic interactions. 相似文献
5.
Single crystal X-ray structural characterizations are recorded for an array of adducts of the form {AgX:[dppc][PF6]}n (n = 1 or 2), [dppc][PF6] = 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate, X = Cl, Br, NO3, NO2, C6H5CO2, CF3CO2. Synthetic procedures for all adducts are reported. All compounds have been fully characterised by elemental analysis and spectroscopic techniques. The structures in the solid state were found to depend on the nature of the counterion, for X = NO3, NO2, the complex being monomeric {[dppc-P,P′]Ag(NO3)2} or {[dppc-P,P′]Ag(NO2)}, for X = Cl, Br, C6H5CO2, CF3CO2, the complex is a dimer. 相似文献
6.
Effendy Fabio Marchetti Riccardo Pettinari Brian W. Skelton 《Inorganica chimica acta》2006,359(5):1504-1512
From the interaction between azole-type ligands L and AgX (X = NO3 or ClO4) or [AgX(PPh3)n] (X = Cl, n = 3; X = MeSO3, n = 2), new ionic mononuclear [Ag(L)2]X and [Ag(PPh3)3L][X] or neutral mono-([Ag(PPh3)nL(X)]) or di-nuclear ([{Ag(PPh3)(L)(μ-X)}2]) complexes have been obtained which have been characterized through elemental analysis, conductivity measurements, IR, 1H NMR and, in some cases, also by 31P{1H} NMR spectroscopy, and single-crystal X-ray studies. Stoichiometries and molecular structures are dependent on the nature of the azole (steric hindrance and basicity), of the counter ion, and on the number of the P-donor ligands in the starting reactants. Solution data are consistent with partial dissociation of the complexes, occurring through breaking of both Ag-N and Ag-P bonds. 相似文献
7.
Euan K. Brechin Ulli Englert Guido Pampaloni Calogero Pinzino 《Inorganica chimica acta》2008,361(8):2375-2384
The synthesis and the characterization of several mono- and dinuclear middle transition metal derivatives of 1,10-phenanthroline-5,6-dione, 1, are presented. The reaction of 1 with CrCl2(THF)2 gives CrCl2(O,O′-C12H6N2O2)(THF)2, 2, while the halides of iron(II), cobalt(II) and nickel(II) afford adducts of general formula MX2(N,N′-C12H6N2O2), M = Fe, 4, Co, 5, X = Cl; M = Ni, 6, X = Br. DFT calculations on CrCl2(L)(THF)2 with L = O,O′-C12H6N2O2 or O,O′-C14H8O2 allowed a direct comparison of the coordination properties of 9,10-phenanthrenequinone and 1,10-phenanthroline-5,6-dione to be made. Dinuclear compounds of general formula CrCl2(THF)2(O,O′-C12H6N2O2-N,N′)MXnLm, M = Zr, 7, X = Cl, n = 4, m = 0; M = Cr, 8, X = Cl, n = 2, L = THF, m = 2; M = Fe, 9, Co, 10, X = Cl, n = 2, m = 0; M = Ni, 11, X = Br, n = 2, m = 0, are prepared from 2 and the corresponding metal halide, while VCp2(O,O′-C12H6N2O2-N,N′)FeCl2, 12, is synthesized by reacting 4 with VCp2. The electronic properties of the different complexes are investigated by magnetic moment measurements and EPR spectroscopy. 相似文献
8.
Christian R. Samanamú 《Inorganica chimica acta》2007,360(14):4037-4043
The reactions of EX3 (E = Ga, In, Tl, X = Br or Cl) with pyrazine and pyrazine, 2-carboxylic acid (pyzca-H) affords a series of one-dimensional ladder polymers, [EX3(pyz)]∞ (E = Ga, In, Tl, X = Cl, Br) and the zigzag polymer [InBr2(OH2)2(pyzca)]∞. These polymers are prepared in high yield through a facile synthesis. The structures of each were characterized in the solid state by single crystal X-ray analysis, infrared spectroscopy and where possible NMR. Experimental results reveal how stability of the one-dimensional polymer increases from gallium to thallium, from the air-sensitive gallium polymer to the aqueous preparation and air-stable products of indium and thallium. 相似文献
9.
Tri(2-methylphenyl)stibine reacts with [PdX2(cod)] or PdX2 (X = Cl or Br) to give the trans-[PdX2{Sb(2-Me- C6H4)3}2]. The single crystal X-ray structures of trans-[PdX2{Sb(2-Me-C6H4)3}2] (X = Cl or Br) revealed that the palladium atom is a square planar environment with mutually trans-Sb(2-methylphenyl)3 ligands. Iodine analogous of complex can also be prepared from trans metallation reaction with sodium iodine. 相似文献
10.
The preparation and characterization of manganese(III) complexes containing the quadridenate ligand, N,N′-bis(aminobenzylidene)-1,2-ethanediamine (H2amben), and its previously unreported analogue, N,N′-bis(2-amino-5-nitro-benzylidene)-1,2-ethanediamine (H2nitroamben), are described. The new manganese(III) halide/pseudohalide complexes, Mn(amben)X · nH2O and Mn(nitroamben)X · nH2O (X = Cl, Br, I, NCS; n = 0.5 or 1), were isolated as red-brown, microcrystalline solids, which were characterized fully. 相似文献
11.
A series of osmium(VI) nitrido complexes containing pyridine-carboxylato ligands OsVI(N)(L)2X (L = pyridine-2carboxylate (1), 2-quinaldinate (2) and X = Cl (a), Br (1b and 2c) or CH3O (2b)) and [OsVI(N)(L)X3]− (L = pyridine-2,6-dicarboxylate (3) and X = Cl (a) or Br (b)) have been synthesised. Complexes 1 and 2 are electrophilic and react readily with various nucleophiles such as phosphine, sulfide and azide. Reaction of OsVI(N)(L)2X (1 and 2) with triphenylphosphine produces the osmium(IV) phosphiniminato complexes OsVI(NPPh3)(L)2X (4 and 5). The kinetics of nitrogen atom transfer from the complexes OsVI(N)(L)2Br (2c) (L = 2-quinaldinate) with triphenylphosphine have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law is obtained: −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) reacts also with [PPN](N3) to give an osmium(III) dichloro complex, trans-[PPN][OsIII(L)2Cl2] (6). Reaction of OsVI(N)(L)2Cl (L = 2-quinaldinate) (2a) with lithium sulfide produces an osmium(II) thionitrosyl complex OsII(NS)(L)2Cl (7). These complexes have been structurally characterised by X-ray crystallography. 相似文献
12.
The reactions of 1 equiv. of the ligand 3-(ethoxycarbonylmethyl-pyridin-2-ylmethyl-amino)-propionic acid methyl ester (2) with the Re(V) starting materials [ReOX3(PPh3)2] (X = Cl, Br) in refluxing chloroform yielded the Re(V)-oxo dihalide complexes [ReOX2{(C5H4NCH2)N(CH2CO2)(C2H4CO2CH3)}] (X = Cl, 3; X = Br, 4). The complexes were characterized by elemental analysis, NMR and IR spectroscopy, cyclic voltammetry and X-ray crystallography. Complex 3 displays distorted octahedral coordination geometry with the tridentate ligand coordinating facially to the Re(V) center. The carboxylate oxygen atom occupies an axial site trans to the ReO bond. The two chlorine atoms consequently adopt a cis configuration. 相似文献
13.
Michael C. Janzen 《Inorganica chimica acta》2005,358(5):1614-1622
The complex [PtMe2(bu2bpy)], 1, bu2bpy = 4,4′-di-t-butyl-2,2′-bipyridine reacts with mercury(II) halides HgX2 (X = Cl, Br, O2CCF3, O2CMe) to give the corresponding complexes [PtMe2X(HgX)(bu2bpy)], 2, by trans oxidative addition followed, when X = O2CCF3, O2CMe only, by easy isomerization to the cis isomers 3. The complexes 2 or 3 react with complex 1 to give the corresponding adducts [PtMe2X(bu2bpy)(μ-HgX)PtMe2X(bu2bpy)], 4, which are shown to contain both covalent and donor-acceptor Pt-Hg bonds in the solid state, and which exhibit very easy fluxionality in solution. 相似文献
14.
Seyyed Javad Sabounchei Hassan Nemattalab Sima Khani Harry Adams 《Inorganica chimica acta》2009,362(1):105-2492
The reactions of phosphorus ylide (p-tolyl)3PCHC(O)CH3 (Y1) with HgX2 (X = Cl and Br) and (p-tolyl)3PCHC(O)C6H4NO2 (Y2) with HgX2 (X = Cl, Br and I) in equimolar ratios using methanol as a solvent are reported. These reactions led to binuclear complexes. C-Coordination of ylides and trans-like structure of complexes [(Y1) · HgBr2]2 and [(Y2) · HgBr2]2 · 2DMSO are demonstrated by single crystal X-ray analyses. The IR, 1H, 13C and 31P NMR data for the other synthesized compounds are similar to the latter complexes, indicating similar structures. Elemental analyses indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in all the products. The ab initio studies indicated that for all dimeric compounds, the observed trans-like structures are 7-10 kcal/mol more stable than the alternative possible cis-like isomers. Although the calculated bond lengths are slightly longer than the measured ones, the similarity of calculated and measured bond angles reflects the similar geometrical structures for these compounds in both the solid state and the gas phase. 相似文献
15.
Claudio Pettinari Fabio Marchetti Alessandro Marinelli Anna Bellusci 《Inorganica chimica acta》2009,362(12):4593-3227
The sterically hindered tetrakis-(3-(p-tolylpyrazolyl)borate [pz0Tpp-Tol] has been prepared and its reaction with CuX2.nH2O (X = Cl or acetate (OAc), M(NO3)2.6H2O (M = Ni, or Co) and MCl2 (M = Zn or Cd) has been investigated. [M(pz0Tpp-Tol)X(Hpzp-Tol)] (M = Cu, X = Cl or OAc; M = Ni or Co, X = NO3) and [M(pz0Tpp-Tol)Cl(Hpzp-Tol)2-n(H2O)n] have been synthesised and their spectroscopic properties described, the five-coordinated Cu species being also structurally characterized. The methyl groups in the para-tolyl fragments of the ligand strongly influences the stoichiometry and structure of the metal complexes. 相似文献
16.
Daniel Bandarra Telma Lopes Marta S. Saraiva Carla D. Nunes Paula Brandão Margarida Meireles Maria José Calhorda 《Journal of inorganic biochemistry》2010,104(11):1171-1177
Several molybdenum complexes, [Mo(η3-C3H5)X(CO)2(N-N)] (N-N = 1,10-phenanthroline, phen: X = CF3SO3T1, X = Br B1, X = Cl C1; N-N = 2,2′-bipyridyl, X = CF3SO3T2, X = Br B2) and [W(η3-C3H5)Br(CO)2(phen)] (W1) have been synthesized and characterized. Their antitumor properties have been tested in vitro against human cancer cell lines cervical carcinoma (HeLa) and breast carcinoma (MCF-7) using a metabolic activity test (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, MTT), leading to IC50 values ranging from 3 to 45 μM, approximately. Most complexes exhibited significant antitumoral activity. Complexes B1 and T2 were chosen for subsequent studies aiming to understand their mechanism of action. Cellular uptake of molybdenum and octanol/water partition assays revealed that both B1 and T2 exhibit a selective uptake by cells and intermediate partition coefficients. The binding constants of B1 and T2 with ct DNA, as determined by absorption titration, are 2.08 (± 0.98) × 105 and 3.68 (± 2.01) × 105 M− 1, respectively. These results suggest that they interact with DNA changing its conformation and possibly inducing cell death, and may therefore provide a valuable tool in cancer chemotherapy. 相似文献
17.
Corrado Di Nicola Claudio Pettinari Brian W. Skelton Allan H. White 《Inorganica chimica acta》2005,358(3):695-706
Single crystal X-ray structural characterizations are recorded for an array of adducts of the form AgX:dppf (1:1)(n), X = simple (pseudo-)halide or oxy-anion, ‘dppf’ = bis(diphenyl phosphino)ferrocene, for adducts X = Cl (new phase), Br, I, SCN, OCN, CN, NO3 (new phase), O2CCH3, n = 2, the form being dimeric [(dppf-P,P′)Ag(μ-X)2Ag(P,P′-dppf)], for X = I, SCN, [Ag(μ-X)2(P-dppf-P′)2Ag′]; for X = O2CCF3, n = ∞, the form is an extended polymer: ?Ag(O · CO · CF3)(P-dppf-P′)Ag′(O?. A dichloromethane solvate phase of CuI:dppf (1:1)2 (also centrosymmetric) is also recorded. Synthetic procedures for all adducts have been reported. All compounds have been characterized both in solution (1H, 13C, 31P NMR, ESI MS) and in the solid state (IR). The topology of the structures in the solid state was found to depend on the nature of the counterion. 相似文献
18.
S. Max Bessey 《Inorganica chimica acta》2010,363(1):279-7422
The synthesis of triethylphosphine gold(I) 4-nitrobenzenethiolate, Et3PAu(SC6H4NO2-4), is reported. Et3PAu(SC6H4NO2-4) displays a low energy visible electronic absorption band which is solvent dependent: EtOH (λmax = 385 nm), acetonitrile (λmax = 391 nm), THF (λmax = 395 nm), and DMSO (λmax = 402 nm). The corresponding low energy visible electronic absorption band of 4-nitrobenzenethiolate, 4-NO2C6H4S− also shows solvent dependency: acetonitrile, (λmax = 484 nm), DMSO (λmax = 502 nm), dimethylformamide (λmax = 505 nm). The positive solvatochromic shifts for Et3PAu(SC6H4NO2-4) and 4-NO2C6H4S− are consistent with an intraligand (IL) charge transfer transition, i.e. π(S) → ∗π (C6H4NO2-4) or n(S) → ∗π (C6H4NO2-4). Assignment of 4-NO2C6H4S− was aided by a DFT calculation. 相似文献
19.
Marcelle de L. Ferreira Thatyana R.A. Vasconcelos Maria C.S. Lourenço James L. Wardell Vitor F. Ferreira 《Carbohydrate research》2009,344(15):2042-2047
Six Schiff base derivatives of d-mannitol, 1,6-dideoxy-1,6-bis-{[(E)-arylmethylidene]amino}-d-mannitol (6: aryl = XC6H4: X = o-, m- and p- Cl or NO2), have been synthesized and evaluated for their in vitro antibacterial activity against Mycobacterium tuberculosis H37Rv using the Alamar Blue susceptibility test and the activity expressed as the minimum inhibitory concentration (MIC) in μg/mL. All three nitro derivatives exhibit significant activities: activities of (6d: X = o-NO2), (6e: X = m-NO2) and (6f: X = p-NO2) are 12.5, 25.0 and 25.0 μg/mL, respectively. When compared with first line drugs, such as ethambutol, they can be considered as a good starting point to develop new lead compounds for the treatment of multidrug-resistant tuberculosis. Characterization of the new compounds 6 is generally achieved spectroscopically. The structure of compound 3 has been confirmed by X-ray crystallography. 相似文献
20.
Seher Tastan 《Inorganica chimica acta》2006,359(6):1889-1898
A new series of square planar palladium(II) complexes with pincer ligands, pip2NCN− (pip2NCNH = 1,3-bis(piperidylmethyl)benzene) and pip2NNN (2,6-bis(piperidylmethyl)pyridine), has been prepared: Pd(pip2NCN)X (X = Cl, Br, I), [Pd(pip2NCN)(L)](BF4) (L = pyridine, 4-phenylpyridine), and [Pd(pip2NNN)Cl]Cl. The X-ray crystal structures of Pd(pip2NCN)Br, [Pd(pip2NCN)(L)]BF4, and [Pd(pip2NNN)Cl]Cl confirm the tridentate coordination geometries of the pincer ligands. For the pip2NCN− complexes, each piperidyl ring adopts a chair conformation with the metal center at an equatorial position on the N(piperidyl) atom. However, one of the piperidyl groups of Pd(pip2NNN)Cl+ adopts a previously unobserved coordination geometry, effectively placing the metal center at an axial position on the N(piperidyl) atom. 1H NMR and UV-Vis absorption measurements provide additional insight into the electronic structures of these complexes. The 1H NMR spectra of Pd(pip2NCN)X (X = Cl, Br, I) are consistent with deshielding of the pip2NCN− ligand resonances along the Cl < Br < I series, in opposition to the relative halogen electronegativities. It is suggested that this trend is consistent with decreasing filled/filled repulsions between the dπ orbitals of the metal center and the lone pair orbitals of the halide ligands along this series. Electronic absorption spectra support the notion that ligand-to-metal charge-transfer states are stabilized in these palladium(II) complexes relative to their platinum(II) analogues. 相似文献