共查询到20条相似文献,搜索用时 15 毫秒
1.
Jian-Qing Tao Zhi-Guo Gu Tian-Wei Wang Qiao-Fang Yang Jing-Lin Zuo Xiao-Zeng You 《Inorganica chimica acta》2007,360(15):4125-4132
Two new spin-crossover complexes, [Fe(Medpq)(py)2(NCS)2] · py · 0.5H2O (1) and [Fe(Medpq)(py)2(NCSe)2] · py (2) (Medpq = 2-methyldipyrido[3,2-f:2′,3′-h]-quinoxaline, py = pyridine), have been synthesized. The crystal structures were determined at both room temperature (298 K) and low temperature (110 K). Complexes 1 and 2 crystallize in the orthorhombic space group Pbca and monoclinic space group P21/n, respectively. In both complexes, the distorted [FeN6] octahedron is formed by six nitrogen atoms from Medpq, the trans pyridine molecules and the cis NCX− groups. The thermal spin transition is accompanied by the shortening of the mean Fe–N distances by 0.194 Å for 2. The mononuclear [Fe(Medpq)(py)2(NCS)2] and [Fe(Medpq)(py)2(NCSe)2] neutral species interact each other via π-stacking, resulting in a one-dimensional extended structure for both 1 and 2. There exist C–HX (X = S, Se) hydrogen bonds for both complexes. Variable-temperature magnetic susceptibility measurements and Mössbauer spectroscopy reveal the occurrence of a gradual spin transition. The transitions are centered at T1/2 = 120 K for 1 and T1/2 = 180 K for 2, respectively. 相似文献
2.
Reaction of the salt KCpCo(CN)3 (1) with zinc iodide leads to the formation of a highly insoluble Co(III)/Zn(II) polymeric chain. However, pyridine was found to disrupt the aggregate that is formed to yield a crystalline trimetallic complex consisting of two CpCo(CN)3 anions bridging a Zn(py)4 dication through the cyanide ligands, [CpCo(CN)2(μ-CN)]2Zn(py)4 (2). Along these same lines, reaction of CpCo(CN)2PPh3 (3) with AlCl3 or CoCl2 leads to the formation of a highly crystalline Co(II)/Co(III) diamond, [CpCo(PPh3)(μ-CN)2CoCl2]2 (4). Molecular structures of 1, 2, 3 and 4 were determined by single-crystal X-ray crystallography. 相似文献
3.
Suzanne Ferrere 《Inorganica chimica acta》2002,329(1):79-92
Ultrafast electron transfer in the dye sensitized solar cell (DSSC) has made it possible to use iron(II) polypyridyl complexes as photosensitizers [J. Am. Chem. Soc. 120 (1998) 843]. Although ruthenium(II) polypyridyl complexes comprise an extensively studied and widely utilized photochemical system, comparatively little is known about the photoproperties of their iron analogues. The syntheses and solution properties of the complexes [FeII(L)2(CN)2] and [FeIIL3] for a series of L, where L is a 2,2′-bipyridine derivative, are presented here. We compare the solvatochromism of [FeII(4,4′-dicarboxylic acid-2,2′-bipyridine)2(CN)2] to [FeII(4,4′-dimethyl-2,2′-bipyridine)2(CN)2] and discuss general trends in the electrochemistry and absorption properties within the series. The solvatochromism of these complexes is discussed in terms of their use in a dye sensitized TiO2 solar cell. 相似文献
4.
In order to assemble polynuclear iron(III) complexes, the coordination chemistry of the 2-hydroxyethyl-3,5-dimethylpyrazole (hedmp-H) ligand has been investigated. Reaction of hedmp-H with trinuclear iron carboxylate precursor [Fe3O(PhCOO)6(H2O)3]Cl in acetonitrile yielded the hexanuclear Fe(III) complex [Fe6O2(OH)2(PhCOO)10(hedmp)2]·3CH3CN (1). This aggregate has been characterized by employing various analytical techniques, spectroscopic studies and single crystal X-ray diffraction. Detailed magnetic susceptibility measurements revealed that 1 displays an ST = 5 ground state. 相似文献
5.
When the iron sulfide complexes (μ-Sx)[CpFe(CO)2]2 (x = 2, 3) are treated with O-alkyl oxalyl chlorides ROCOCOCl the complexes CpFe(CO)2SCOCO2R (1) [R = Me (a), Et (b)] are obtained. Similarly, the complexes CpFe(CO)2SeCOCO2R (2) are obtained from the analogous iron selenide (μ-Se)[CpFe(CO)2]2 reaction with the same reagents. Treatment of the iron selenide with half equivalent of oxalyl chloride produces the dimeric complex [CpFe(CO)2SeCO]2 (3). The new complexes, 1, 2 and 3, have been characterized by elemental analyses, IR and 1H NMR spectroscopy. The solid state structures of 1a, 2a, 3 and [CpFe(CO)2SCO]2 (4) were determined by an X-ray crystal structure analysis. 相似文献
6.
Vladimir P. Fedin Irina V. KalininaAndrey Gerasimenko Alexander V. Virovets 《Inorganica chimica acta》2002,331(1):48-51
Dark-brown single crystals of the title compound 1 were obtained in high yield by layering a CuCl2 solution in 25% aqueous ammonia on a glycerol solution of K6[W4Te4(CN)12]·5H2O. The complex 1 was characterized by single crystal X-ray diffraction analysis and IR spectroscopy. The X-ray structure of 1 reveals a polymeric chain cyano-bridged cluster-metal coordination compound. The [W4Te4(CN)12]6− cluster anions are linked one to another by Cu2+ cations through coordination by nitrogen atoms of the CN groups. 相似文献
7.
Janusz Szklarzewicz Dariusz Matoga Krzysztof Lewiński 《Inorganica chimica acta》2007,360(6):2002-2008
Ligand-field photolysis of K4[Mo(CN)8] · 2H2O in 98% N2H4 · H2O yields the catalytical decomposition of N2H4 into NH3 and N2. From irradiated solutions of octacyanomolybdate(IV) both in NH3(aq) and 98% N2H4 · H2O(l) as solvents, the salt of the formula (PPh4)2[Mo(CN)4O(NH3)] · 2H2O was isolated. The salt is not formed by direct ligand replacement in tetracyanooxomolybdate(IV) ions derived from K3Na[Mo(CN)4O2] · 6H2O as the solute in similar conditions. The X-ray crystal structure and spectral properties of (PPh4)2[Mo(CN)4O(NH3)] · 2H2O are described. The improved method of the synthesis of K4[Mo(CN)8] · 2H2O is also presented. 相似文献
8.
A series of cuboidal iron-sulfur clusters [Fe4S3(NO)4(PR3)3]0,1+ (R = Et, Pri, Cy) were synthesized by two routes: reductive desulfurization of [Fe4S4(NO)4] by tertiary phosphines, and substitution of triphenylphosphine in [Fe44S3(NO)4(PPh3)3] by a more basic phosphine. The structures of 3[Fe4S3(NO)4(PEt3)3] · 0.5Et2O, [Fe4S3(NO)4(PEt3)3] [Fe4S3(NO)7] and partially substituted [Fe4S3(NO)4(PPh3)2− (PPri3)] have been determined by X-ray diffraction in order to define the cuboidal Fe4S3 core, previously known only in Roussin's black anion and its reduced form, [Fe4S3(NO)77]1−,2−, and as a part of the iron-molybdenum cofactor of nitrogenase. 相似文献
9.
Cristina Femoni Maria Carmela Iapalucci Giuliano Longoni Per H. Svensson 《Inorganica chimica acta》2002,330(1):111-117
The reaction of [N(PPh3)2]2[Ni6(CO)12] with Cu(PPh3)xCl (x=1, 2), as well as the degradation of [N(PPh3)2]2[H2Ni12(CO)21] with PPh3, affords the new and unstable dark orange–brown [N(PPh3)2]2[Ni9(CO)16].THF salt in low yields. This salt has been characterized by a CCD X-ray diffraction determination, along with IR spectroscopy and elemental analysis. The close-packed two-layer metal core geometry of the [Ni9(CO)16]2− dianion is directly related to that of the bimetallic [Ni6Rh3(CO)17]3− trianion and may be envisioned to be formally derived from the hcp three-layer geometry of [Ni12(CO)21]4− by the substitution of one of the two outer [Ni3(CO)3(μ−CO)3]2− layers with a face-bridging carbonyl group. 相似文献
10.
M.S Papadopoulos P Bouziotis I.C Pirmettis C.P Raptopoulou A Terzis E Chiotellis 《Inorganica chimica acta》1999,290(2):2808-250
A novel five-coordinate rhenium(III)-thiolato complex, Re(SCH2C6H4OCH3-p)3(PPh3)2 has been isolated during the reaction of trans-ReOCl3(PPh3)2 with p-methoxybenzyl mercaptan. In the unexpected structure that was acquired, the central metal has undergone a reduction from Re(V) to Re(III). The five-coordinate Re(III) complex has been characterized by spectroscopic methods, elemental analysis and X-ray crystallography. X-ray crystallographic studies showed the coordination geometry around rhenium to be that of a trigonal bipyramid. The basal plane is defined by three sulfur atoms of the monodentate ligand, while the two apical positions are occupied by two phosphines of the precursor. 相似文献
11.
The novel ferromagnetic coupling one-dimensional complex {Cu(NIT3Py)2[N(CN)2]2(H2O)2} (NIT3Py=2-(3′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group C2/c. The Cu(II) ion is in a distorted octahedral environment. The units of {Cu(NIT3Py)2[N(CN)2]2(H2O)2} were connected as one-dimensional structure by the intermolecular hydrogen bonds. Magnetic measurements show that there are intramolecular ferromagnetic interactions and intermolecular antiferromagnetic interactions within the chain. 相似文献
12.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4. 相似文献
13.
Oliver Renn Heinz Rüegger Luigi M. Venanzi Jürgen Gallus Volker Gramlich Arianna Martelletti 《Inorganica chimica acta》1995,240(1-2):575-580
It is shown that the reaction of RhCl3·3H2O with acetonitrile normally produces mixtures of mer- and fac-[RhCl3(CH3CN)3] (1a and 1b, respectively). The IR and 1H NMR spectra of these isomers were re-investigated. Their two-dimensional (103Rh,1H) NMR spectra were also recorded. Equilibrium and exchange studies of 1a and 1b in CD3C were performed. It was found that in 1a the exchange rate of the nitrile molecule trans to Cl is much faster than those of mutually trans nitriles. Also the nitrile molecules in 1b underwent fast exchange in CD3CN; however, their rate was slightly faster than that of the more labile CH3CN in 1a. The X-ray crystal structure of mer-[RhCl3(CH3CN)3]·CH3CN (1c) was determined. Crystal data: triclinic space group . 相似文献
14.
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
15.
The crystal structure of the title compound [Fe(bpz)3](ClO4)2 · H2O (bpz=2,2′-bipyrazine) has been determined by a single crystal X-ray diffraction study at 293(2) K. The complex is monoclinic, P21/c, a=17.263(3), b=9.983(2), c=17.921(4) Å, β=107.94(3)°, V=2938.3(10) Å3, Z=4, R=0.073 and Rw=0.118. The structure is made up of tris-chelated [Fe(bpz)3]2+ cations, uncoordinated perchlorate anions and crystallization water molecules. The iron atom exhibits a FeN6 distorted octahedral geometry with average Fe-N bond length and N-Fe-N bidentate angle of 1.962(5) Å and 81.6(2)°. The value of the Fe-N bond distance and that of the room temperature magnetic moment are in agreement with a singlet 1A1 ground state. The structure of 1 is compared to those of other tris-chelated iron(II) complexes with bidentate nitrogen heterocycles. 相似文献
16.
A new complex of composition [Cu(2-NO2bz)2(nia)2(H2O)2] (1) (nia = nicotinamide, 2-NO2bz = 2-nitrobenzoate) has been prepared and its composition and stereochemistry as well as coordination mode have been determined by elemental analysis, electronic, infrared and EPR spectroscopy, magnetization measurements over the temperature range 1.8-300 K, and its structure has been solved, as well. The complex structure consists of the centrosymmetric molecules with Cu(II) atom monodentately coordinated by the pair of 2-nitrobenzoato anions and by the pair of nicotinamide molecules, forming nearly tetragonal basal plane, and by a pair of water molecules that complete tetragonal-bipyramidal coordination polyhedron about the copper atom. The complex 1 exhibits magnetic moment μeff = 1.86 B.M. at 300 K which decreases to μeff = 1.83 B.M. at 1.8 K. The magnetic susceptibility temperature dependence obeys Curie-Weiss law with Curie constant of 0.442 cm3 K mol−1 and with Weiss constant of −1.0 K. EPR spectra at room temperature as well as at 77 K are of axial type with g⊥ = 2.065 and g∥ = 2.280 and exhibit clearly, but partially resolved parallel hyperfine splitting with AII = 160 G, that is consistent with the determined molecular structure of 1. In order to analyze the factors influencing the degree of tetragonal distortion of coordination polyhedron, the dataset of 72 structures similar to that of 1 was extracted from CCD and analyzed. A significant correlation between the average Cu-Oax bond length and tetragonality parameter τ which was found as a consequence of the Jahn-Teller effect. 相似文献
17.
The organometallic Lewis acid, [CpFe(CO)2]+ (Cp = η5-C5H5) reacts with excess dry diethyl ether at low temperatures to form the labile complex [CpFe(CO)2(Et2O)]+[BF4]− (1) which is stable at low temperatures and has been fully characterized. Complex 1 in turn reacts with 1-aminoalkanes and α,ω-diaminoalkanes to form new complexes of the type [CpFe(CO)2NH2(CH2)nCH3]BF4 (n = 2-6) (2) and [{CpFe(CO)2}2μ-(NH2(CH2)nNH2)](BF4)2 (n = 2-4) (3), respectively. These complexes have been fully characterized and the mass spectral patterns of complexes 2 are reported. The structures of compounds 2a (n = 2) and 2b (n = 3) have been confirmed by single crystal X-ray crystallography. The single crystal X-ray diffraction data show that complex 2a, [CpFe(CO)2NH2(CH2)2CH3]BF4, crystallizes in a triclinic space group while 2b, [CpFe(CO)2NH2(CH2)3CH3]BF4, crystallizes in an orthorhombic Pca21 space group with two crystallographically independent molecular cations in the asymmetric unit. Furthermore, the reaction of 1 with 1-alkenes gives the η2-alkene complexes in high yield. 相似文献
18.
The reaction of cis- or trans-[Ru(CNtBu)4(CN)2] with Fe(III) compounds leads to the formation of molecular squares of the general formula cyc-[Ru(CN-tBu)4(CN)2FeX3]2 or one-dimensional coordination polymers [Ru(CN-tBu)4(CN)2FeX3]n, respectively. Temperature dependent susceptibility measurements indicate that the magnetic properties of the coordination compounds are determined by their molecular structure. Of particular importance is the local symmetry at the iron(III) center which is related to the coordinating anion. The magnetic properties are best described in terms of weak antiferromagnetic interactions between the iron centers for the molecular squares as well as the coordination polymer with X = NO3 and as weak ferromagnetic interactions in case of the linear coordination polymer with X = Cl. For all compounds zero field splitting at low temperatures has to be taken into account. 相似文献
19.
J.A. García-Vázquez J. Romero R. Castro A. Sousa D.J. Rose J. Zubieta 《Inorganica chimica acta》1997,260(2):2900-223
(3-Trimethylsilyl-pyridine-2-thiolato-S,N)copper(I), [Cu(3-Me3Sipyt)], was obtained by electrochemical oxidation of copper metal in an acetonitrile solution of the neutral ligand. The compound is tetrameric and the four copper atoms are arranged with distorted tetrahedral geometry, each copper atom being trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 141/a, a=14.608(2), C=19.366(4) Å, V=4133(2), Å, Z=4, Dcalc=1.581 g cm−3, R=0.0397 for 848 reflections. 相似文献
20.
Bimetallic alkylidene complexes of molybdenum (RF3O)2(ArN)MoCH-SiMe2-CHMo(NAr)(ORF3)2 (1) and (RF3O)2(ArN)MoCH-SiPhVin-CHMo(NAr)(ORF3)2 (2) (Ar = 2,6-C6H3; RF3 = CMe2CF3) have been prepared by the reactions of vinyl silicon reagents Me2Si(CHCH2)2 and PhSi(CHCH2)3 with known alkylidene compound PhMe2C-CHMo(NAr)(ORF3)2. Complexes 1 and 2 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1 and 2 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and predominant cis-units content in the case of 2. 相似文献