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1.
Red or orange crystals of [Co(NH3)6]2Cl2[Fe(CN)6] · 4H2O (1), [Co(en)3]2Cl2[Fe(CN)6] · 2H2O (2) and [Co(en)3]4[Fe(CN)6]3 · 21.6H2O (3) were isolated from the aqueous systems Co3+-LN-[Fe(CN)6]4− (LN = NH3, en = 1,2-diaminoethane). In all isolated samples the combination of Mössbauer (δ values were from the range −0.07 to −0.08 mm/s) and IR spectra (ν(CN) stretching vibrations in the range 2015-2047 cm−1) confirms the presence of low spin Fe(II) in [Fe(CN)6]4− anions. X-ray structure analyses corroborate the ionic character of all studied compounds. These contain diamagnetic [Co(NH3)6]3+ (1) or [Co(en)3]3+ (2 and 3) complex cations and diamagnetic [Fe(CN)6]4− complex anions. In compounds 1 and 2 chloride anions are present, too. All three compounds contain water of crystallization, in compound 3 as many as 21.6 molecules per formula unit. 相似文献
2.
Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)4]2− (NN = 2,2′-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)4]2− salts, in the formation of small amounts of salts of the dinuclear species [Ru2(NN)2(CN)7]3−. These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)4]2− following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H2O)5.5][Ru2(bipy)2(CN)7] · 11H2O and [Pr(H2O)6][Ru2(phen)2(CN)7] · 9H2O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru2Ln2(μ-CN)4 squares and Ru4Ln2(μ-CN)6 hexagons, which alternate to form a one-dimensional chain. In [CH6N3]3[Ru2(bipy)2(CN)7] · 2H2O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru2(NN)2(CN)7]3− anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4′-tBu2-2,2′-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH6N3]2[Ru(tBu2bipy)(CN)4] · 2H2O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru2(phen)2(CN)7]3− could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)4]2− if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru2(bipy)2(CN)7]3− (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)4]2−, with a 3MLCT emission at 581 nm. 相似文献
3.
Junhua LuoMaochun Hong Changzhang ChenMaoxiang Wu Dongshou Gao 《Inorganica chimica acta》2002,328(1):185-190
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions. 相似文献
4.
Zhe-Ming WangBai-Wang Sun Jun LuoSong Gao Chun-Sheng LiaoChun-Hua Yan Yong Li 《Inorganica chimica acta》2002,332(1):127-134
Two novel bimetallic coordination polymers, [Cu(en)2][Mn(dca)4] (1) and [Cu(pn)2][Mn(dca)4] (2) (en, ethylenediamine; pn, 1,3-diaminopropane; dca, dicyanamide N(CN)2−), have been synthesized and characterized. Both of them consist of Mndca anionic chains and chelate cations of copper. 1 has a sheet like architecture built by the [Cu(en)2]2+ cations and the homoleptic trans-[Mn(dca)4 2−]n chains. 2 shows unusual 3-D threefold interpenetrating diamond-like structure constructed by [Cu(pn)2]2+ cations and the homoleptic cis-[Mn(dca)4 2−]n chains. The magnetic susceptibilities obey the Curie-Weiss law with weak antiferromagnetic interactions. 相似文献
5.
Four novel imidazolium salts, precursors to N-heterocyclic carbene (NHC) ligands, with 2,5-dimethoxybenzyl or 2,5-dihydroxybenzyl (i.e., p-hydroquinone) substituents have been prepared. The crystal structure of the hydroquinone-substituted imidazolium salt H3L3Br reveals Br−?H-O bridged chiral chains of alternating [H3L3]+ cations and Br− counter-ions parallel to the x-axis. Palladium(II) complexes were accessible from reactions of the dimethoxyphenyl-substituted imidazolium precursors with palladium(II) acetate, but not from reactions of imidazolium cations with hydroquinonyl substituents. The crystal structure of the bis(dimethoxybenzyl)-substituted bis(NHC)Pd complex, cis-[PdBr2(L2)] (2), is described. Puckering of the bis(NHC) ligand leads to a cleft in which an included molecule of dimethylformamide is situated. The cleft is closed by one of the dimethoxybenzyl groups which π-stacks with the dimethylformamide; the other dimethoxybenzyl group points away from the cleft and Pd(II) centre. Reaction of complex 2 with BBr3 afforded the targeted bis(hydroquinone)-substituted bis(NHC)Pd(II) complex 3 (97% yield) which, in turn, was oxidised by 2,3-dichloro-5,6-dicyano-benzoquinone to the corresponding p-benzoquinone-substituted bis(NHC)Pd(II) complex 4 (98% yield). The cyclic voltammograms of the Pd(II) complexes 2-4 reveal waves that are attributed to an admix of the anticipated ligand-centred and [Pd(C-NHC)2Br2]-centred processes. 相似文献
6.
Two new charge transfer salts of TTF with the counter anions [M(phen)(CN)4]− (phen = 1,10-phenanthroline, M = Cr (I) and Fe (II)) are described. The structures consist of alternating stacks of dimerised TTF+ cations and [M(phen)(CN)4]− anions and they are linked together by many short S?S contacts and hydrogen bonds. Within the organic stack, two dimerised TTF+ cations are arranged in a slipped face-to-face mode with short intra-dimer and long inter-dimer S?S distances. Strong antiferromagnetic exchange was found in the TTF+ dimers. Conductivity measurements show that compound I is a semiconductor. 相似文献
7.
《Inorganica chimica acta》2004,357(4):1219-1228
The new mononuclear [FeCl2(HOPri)4] (1), polymeric [{Cl3Fe(μ-Cl)Fe(HOPri)4}n] (2) and binuclear [I2Fe(μ-I)2Fe(PriOH)4] (3) iron(II) complexes have been synthesized in high yields in propan-2-ol or toluene/propan-2-ol mixtures at room temperature. Magnetic moment measurements, 57Fe Mössbauer spectroscopy data and the results of semi-empirical quantum mechanical calculations confirmed the high-spin configuration of the iron(II) centres, which were shown to be four- and/or six-coordinate by single crystal X-ray diffraction analyses. Intermolecular hydrogen bonding was observed in the solid state structure of 1, intramolecular interactions in 2, while both intra- and intermolecular association was seen in 3. Long iron-(μ-halide) bonds suggest the possibility of complex dissociation in solution and facile ligand substitution in 2 and 3. 相似文献
8.
The syntheses of the aliphatic bidentate guanidine-amine-hybrid ligands DMEGdmae (L1), TMGdmae (L2), TMGdeae (L3) and DPipGdmae (L4) as well as the reaction of their Cu(I) complexes with molecular oxygen (monitored by UV-Vis spectroscopy) are reported. The molecular structures of 10 bis(μ-hydroxo) dicopper complexes based on these ligands are described. The solid state structures of [Cu2(μ-OH)2(DMEGdmae)2]X2 (X− = I− (1), CF3SO3− (2), SbF6− (3), PF6− (4)), [Cu2(μ-OH)2(TMGdmae)2]X2 (X− = I− (5), CF3SO3− (6)), [Cu2(μ-OH)2(TMGdeae)2]Cu2I4 (7) and [Cu2(μ-OH)2(DPipGdmae)2]X2 (X− = CF3SO3− (8), SbF6− (9), PF6− (10)) show a square-planar distorted coordination of the copper(II) ion. The bis(μ-hydroxo) dicopper complex 1 exhibits a Cu···Cu distance of 2.860(1) Å, which is one of the smallest observed for hydroxo-bridged copper compounds so far. The influence of the anion on the structure of the bis(μ-hydroxo) dicopper(II) unit is analyzed for the reported complexes and a literature overview with emphasis on the structural characteristics of the Cu2O2 moiety of bis(μ-hydroxo) dicopper(II) and bis(μ-oxo) dicopper(III) is given. 相似文献
9.
The synthesis of [K]2[CpFe(CN)3] (1) and its pentamethylcyclopentadienyl analog (2) has been described via the photolysis of the corresponding [K][CpFe(CO)(CN)2] salts in methanol in the presence of KCN. The structure of complex 1 has been characterized by means of X-ray crystallography, where the potassium ions are interacting with the N atoms of the cyanide ligands. As expected, the average νCN stretching frequency in the anion is 16 cm−1 higher than that in the more electron-donating pentamethylcyclopentadienyl derivative. 相似文献
10.
Christophe Faulmann Stéphane Dorbes Kane Jacob Gábor Molnár José Antonio Real 《Inorganica chimica acta》2007,360(13):3870-3878
A new compound of formula [Fe(qsal)2][Ni(dmit)2] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit2− = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)2]-based complexes, and more particularly [Fe(qsal)2][Ni(dmit)2] · 2CH3CN. 相似文献
11.
The reaction of FeCl3 · 6H2O, potassium hydrotris(pyrazolyl)borate (KTp) and KSCN gives [FeTp2][TpFe(NCS)3] (1) and [FeTp2]3[Fe(NCS)6] (2), respectively. The bond lengths and angles indicate that both complexes have [FeTp2]+ cations where Fe(III) ions are in typical low-spin state, and in counter ions, [TpFe(NCS)3]− for 1 and [Fe(NCS)6]3− for 2 are both in high-spin state. Variable temperature magnetic susceptibility and ESR results also show that there are double spin states of iron(III) ions within the crystal lattice of both compounds. 相似文献
12.
Silvia Melnic Charles Simmons Tatiana Chiriac Valeriu Rudic 《Inorganica chimica acta》2011,373(1):167-172
New trinuclear iron(III) furoates with the general formula [Fe3O(α-fur)6(R-OH)3]X, where α-fur C4H3OCOO, R = CH3 (1), C2H5 (2), n-C3H7 (3), n-C4H9 (4), X = NO3− (1-4); [Fe3O(α-Fur)6(DMF)(CH3OH)2]NO3 (5); [Fe3O(α-Fur)6(H2O)(CH3OH)2]Cl (6); [Fe2MO(α-Fur)6(L)(H2O)2], where L = THF (7-9), DMF (10-12), M = Mn2+ (7, 10), Co2+ (8, 11), Ni2+ (9, 12) and [Fe2MO(α-Fur)6(3Cl-Py)3], where M = Mn2+ (13), Co2+ (14), Ni2+ (15); have been prepared and investigated by Mössbauer and IR spectroscopy. The X-ray crystal structure for the 1·2CH3OH complex indicates that it crystallizes in the monoclinic crystal system (P21/n) and has a structure typical of μ3-O-bridged trinuclear iron(III) compounds. Coordination compounds 1, 4, 7, 8 can be used as regulators of the biochemical composition of cyanobacterium Spirulina platensis biomass. The supplementation of these compounds, in concentrations exceeding 5-10 mg/l, increases the content of iron, amino acids, peptides and carbohydrates in Spirulina. 相似文献
13.
Val Phillips Tania Lasanta Jeffrey W. Bacon Arnold L. Rheingold 《Inorganica chimica acta》2010,364(1):195-204
A comparative study of metallophilic interactions of [Pt(tpy)X]+ cations (tpy = 2,2′:6′,2″-terpyridine) in the presence of two different types of anions, (i) []− anions that form double salts and (ii) simple p-block anions, is reported. Single-crystal X-ray diffraction data, solution-state 195Pt NMR spectra, and variable temperature solid-state luminescence spectra are reported. Three [Pt(tpy)Cl]Y derivatives (Y = SbF6, 1, SbF6·CH3CN, 4, PF6, 2) and the [Pt(tpy)Br]PF6 analog, 3, as well as two new double salts [Pt(tpy)CN][Au(CN)2], 5, and [Pt(tpy)CN]2[Au(C6F5)2](PF6), 6, have been synthesized and characterized. Structural analysis shows consistent patterns in Pt···Pt interactions that vary slightly depending on the coordinating halogen or pseudo-halogen X, counter anion Y, and lattice solvent. Metallophilic interactions are seen between [Pt(tpy)X]+ cations with all types of X ligands, but only with π-accepting X′ ligands from []− anions are Pt?Au metallophilic interactions seen to be favored over Pt?Pt interactions. The [Au(CN)2]− anion consistently forms Pt···Au metallophilic contacts, unlike [Au(C6F5)2]−. The 195Pt NMR chemical shifts are ∼−2750 ppm for π-donor ligands and near −3120 ppm for π-acceptor ligands in [Pt(tpy)X]PF6 compounds. Luminescence data show an unusual blue shift in [Pt(tpy)CCPh][Au(C6F5)2] versus [Pt(tpy)CCPh]PF6 ascribed to an intermolecular charge transfer. 相似文献
14.
Six new bromothallate(III)-containing salts with different alkyl diammonium cations have been prepared from bromide containing solutions and studied by single-crystal X-ray crystallographic analyses. The N,N′-diethyl-N,N,N′,N′-tetramethyl-1,2-ethylenediammonium, N-methyl-1,3-propanediammonium, N,N,N′,N′-tetramethyl-1,3-propanediammonium and N,N,N′,N′-tetraethyl-1,2-ethylenediammonium cations yield complexes (I, II, III and IV, respectively) with the [TlBr5]2− anionic stoichiometry. For I and II, both complexes contain the [TlBr5]2− anion. In complex II, this appears as a distorted octahedron with one long Tl?Br2′ contact of 3.632(4) Å from an adjacent anion, thus completing the hexacoordination about an otherwise distorted square pyramid. On the other hand, for III and IV, both complexes contain a tetrahedral [TlBr4]− anion together with an isolated, but hydrogen-bonded, Br− anion. The 1,5-hexanediammonium complex (V) contains tetrahedral [TlBr4]−, slightly distorted octahedral [TlBr6]3− and Br− anions. The asymmetric unit of the N,N-diethyl-1,3-propanediammonium salt (VI) contains one cation and half of each of a [TlBr4]− and an axially compressed octahedral [TlBr6]3− anion. Extensive hydrogen-bonded networks exist in complexes II-VI. NH?Br hydrogen bonds generally have a significant influence on the nature of the anions present in species with the formal [TlBr5] stoichiometry. 相似文献
15.
In an unusual reaction of [RuIII(acac)2(CH3CN)2](ClO4) ([1], acac = acetylacetonate) and aniline (Ph-NH2), resulted in the formation of ortho-semidine due to dimerisation of aniline via oxidative ortho-Carom-N bond formation reaction. This oxidation reaction is associated with stepwise chlorination of coordinated acac ligands at the γ-carbon atom resulting in the formation of [RuIII(acac)2L−] [2a], [RuIII(Cl-acac)(acac)L−] [2b], [RuIII(acac)(Cl-acac)L−] [2c] and [RuIII(Cl-acac)2L−] [2d] (L− = N-phenyl-ortho-semiquinonediimine) complexes, respectively. These have been characterized by 1H NMR, UV-Vis-NIR, ESI-MS and cyclic voltammetry studies. Single crystal X-ray structures of 2c and 2d are reported. Crystallographic structural bond parameters of 2c and 2d revealed bond length equalization of C-C, C-O and M-O bonds. It has been shown that perchlorate () counter anion, present in the starting ruthenium complex, acts as the oxidizing agent in bringing about oxidation of Ph-NH2 to ortho-semidine. The chloronium ions, produced in situ, chlorinate the coordinated acac ligands at the γ-carbon atom. Such electrophilic substitution of coordinated acac ligands indicates that the Ru-acac metallacycles in the reference compounds are aromatic. The complexes showed an intense and featureless band centered near 520 nm, and a structured band near 275 nm. These displayed one reversible cathodic response in the range, −1.1 to −0.8 V and one reversible anodic response between 0.4 and 0.6 V versus the Saturated Calomel reference Electrode, SCE. The response at the anodic potential is due to oxidation of the coordinated ligand L, while the reversible response at cathodic potential is due to reduction of the metal center. 相似文献
16.
Using an anionic precursor [(Tp)FeIII(CN)3]− (1) as a building block, two cyano-bridged centrosymmetric heterotrinuclear complexes, (2) and (3) (en = ethylenediamine), have been synthesized and structurally characterized. In each complex, [TpFe(CN)3]− acts as a monodentate ligand toward a central [Mn(C2H5OH)4]2+ or [Ni(en)2]2+ core through one of its three cyanide groups, the other two cyanides remaining terminal. The intramolecular Fe-Mn and Fe-Ni distances are 5.2354(4) and 5.0669(11) Å, respectively. The magnetic properties of complexes 2 and 3 have been investigated in the temperature range of 2.0-300 K. A weak antiferromagnetic interaction between the Mn(II) and Fe(III) ions has been found in complex 2. The magnetic data of 2 can be fitted with the isotropic Hamiltonian: where J and J′ are the intramolecular exchange coupling parameters between adjacent and peripheral spin carriers, respectively. This leads to values of J = −1.37 cm−1 and g = 2.05. The same fitting method is applied to complex 3 to give values of J = 1.2 cm−1 and g = 2.25, showing that there is a ferromagnetic interaction between the Fe(III) and Ni(II) ions. 相似文献
17.
Xiang-Yong Lu 《Inorganica chimica acta》2009,362(14):5113-2011
Two tetra-nuclear Ag(I) complexes with styrene-functionalized N-heterocyclic carbene [AgL2]2[Ag2X4] (L = 1-methyl-3-(4-vinylbenzyl)imidazol-2-ylidene, X = Cl, 2a; X = I, 2b) were prepared by the reactions between the corresponding imidazolium salts with Ag2O. The reaction mixture was further treated with AgBF4 to give a mononuclear ion-pair complex [AgL2][BF4] (3). The molecular structures of these new Ag(I) complexes have been determined by X-ray diffraction analyses. 2a and 2b consist of two [Ag(L)2]+ fragments with the central [Ag2X4]2− anion held together by the close Ag(I)-Ag(I) interactions. Complex 3 is a mononuclear ion-pair complex with a linear bi-coordinate Ag fragment. 相似文献
18.
Two novel molecular magnetic materials, [RBzTPP][Ni(mnt)2] (mnt2− = maleonitriledithiolate, [RBzTPP]+ = 4-R-benzyltriphenylphosphinium; R = CN (1), Cl (2)) were synthesized and characterized by X-ray diffraction, IR spectroscopy, and magnetic susceptibility measurements. In crystal of 1, the [Ni(mnt)2]− anions form a dimer via Ni?S and π?π stacking interactions between Ni(mnt)2 planes, and the C-H?Ni and C-H?N H-bonding interactions are found between the [Ni(mnt)2]− anions and the neighboring [CNBzTPP]+ cations. The anions and cations of 2 stack into well-segregated columns in the solid state; and the Ni(III) ions form a 1D alternating chain in a Ni(mnt)2 column through intermolecular Ni?S, or π?π interactions with the Ni?Ni distances of 3.900, 4.198, and 4.165 Å. Magnetic susceptibility measurements for these complexes in the temperature range 1.8-300 K show that the overall magnetic behavior for 1 and 2 indicates the presence of antiferromagnetic interaction, but 1 exhibits an activated magnetic behavior in the high-temperature (HT) region together with a Curie tail in the low-temperature (LT) region. 相似文献
19.
Brian T. Heaton Jonathan A. Iggo Vadim I. Ponomarenko Sergey P. Tunik 《Inorganica chimica acta》2010,363(3):549-554
Addition of excess CF3CO2H (HTFA) to [Rh2Pt2(CO)7(PPh3)3], I, under nitrogen results in the formation of a salt (X2+ Y2−), which contains only the second example of a di-cationic carbonyl hydride tetra-nuclear cluster, [H2Rh2Pt2(CO)7(PPh3)3]2+, X2+, and a presently partially characterized polymetallic anion Y2−. The di-cation X2+ has been characterized by mass spectrometry and a variety of multinuclear NMR methods. Since there is no difference in the electron count for I and X2+, it is probable that both I and X2+ adopt similar butterfly metallic frameworks with a Rh-Rh hinge; in X2+, there are two bridging hydrides to the same wing-tip Pt but the phosphine site occupancies on the Rh2Pt2-framework in I and X2+ are different. 相似文献
20.
Ulrich Jürgen Scheele 《Inorganica chimica acta》2006,359(15):4891-4900
A series of six 3,6-bis(imidazolium-3-yl)pyridazine derivatives with different imidazole-N substituents have been synthesized and isolated as the salts [H2L]Cl2 (1a)-(6a) and [H2L](PF6)2 (1b)-(6b). Solid state structures have been determined crystallographically for eleven out of the twelve compounds, revealing diverse hydrogen bonding patterns that involve the imidazolium-C2H units and the anions. N-heterocyclic carbene (NHC) mercury(II) complexes [Hg2L2](PF6)4 (7)-(9) are readily formed in good yields from ligand precursors [H2L](PF6)2 and Hg(OAc)2, as long as imidazole-N substituents are not too bulky. X-ray crystallography reveals double helical bimetallic arrangements for the stable [Hg2L2]4+ cations. Ligand scrambling in [Hg2L2]4+ occurs only in the presence of free carbene precursor, presumably via an associative mechanism. 相似文献