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1.
Phenol, having favourable physical and chemical properties, can be enclosed as the guest component in the clathrates of tetracyano complexes. Six compounds of Hofmann and similar type clathrates M(NH3)2M' (CN)4.nG and M(en)m M'(CN)4.nG were prepared and identified: Ni(NH3)2Pt.2C6H5OH; Ni(en)2Pt(CN)4.O.14C6H5OH; Ni(NH3)2Pt(CN)4.C6H5OH.H2O; Zn(NH3)2Ni(CN)4.O.1C6H5OH.H2O; Cu(NH3)2Ni(CN)4. 2C6H5OH and Fe(NH3)2Ni(CN)4.2C6H5OH. The phenol containing clathrates are more stable than clathrates containing other guest molecules. In the case of Ni(en)2 Pt(CN)4.O.14C6H5OH thermal loss of the guest molecule leaves the host lattice intact, but further heating results in the rupture of the host lattice. The compounds were capable in the solid state of sorbing other organic molecules once they had been heated to the temperature required for almost complete loss of guest molecule i.e. n→o.  相似文献   

2.
Hofmann's benzene clathrate Ni(NH3)2Ni(CN)4·2C6H6 suspended in ammoniacal, neutral, and acidic aqueous media undergoes the replacement reactions of the guest C6H6 and the ligating NH3 molecules with molecules of water to give Ni(NH3)2Ni(CN)4·?1H2O, Ni(H2O)2Ni(CN)4·nH2O(0<n<2), and Ni(H2O)2Ni(CN)4·4~5H2O, respectively. The integrity of the host metal complex sheet structure is conserved with little change during the replacement reactions.  相似文献   

3.
The time-dependent changes which are observed in the infrared and Raman spectra of samples of the two Hofmann aniline clathrates M(NH3)2Ni(CN)4.an2 {M = Cd(II), Ni(II), an = C6H5NH2} indicate the occurrence of a solid state ligand replacement reaction in which the aniline guest molecule replaces the coordinated ammonia to give Man2Ni(CN)4 as the final product. The rate of replacement is greater for the cadmium than for the nickel clathrate, and for both clathrates evacuation of the sample greatly increases the rate of replacement. The Man2Ni(CN)4 complexes can themselves act as host lattices forming clathrates containing guest molecules such as aniline.  相似文献   

4.
Infrared spectra of Mn(NH3)2M(CN)4·2C6H5NH2 (M = Zn, Cd or Hg) are reported. The spectral data suggest that these compounds are similar in structure to Hofmann-Td-type clathrates.  相似文献   

5.
Infrared spectra of M(1,10-diaminodecane)Ni(CN)4 · 1,5 G (M=Co, Ni or Cd; G=o-xylene, m-xylene, p-xylene) and Cd(l,6-diaminohexane)M(CN)4 · C6H6 (M=Cd or Hg) clathrates are reported. The 1,10-diaminodecane and 1,6-diaminohexane molecules in the host permit the inclusion of bulky guest molecules. The spectral data of clathrates were compared with those of the corresponding host. The spectral features suggest that these compounds are similar in structure to other Hofmann-type and Hofmann-Td type clathrates, respectively.  相似文献   

6.
Two new cadmium dimethylpyrazine (2,3-dimethylpyrazine or 2,5-dimethylpyrazine) tetracyanonickelate benzene clathrates, [Cd(C6H8N2)Ni(CN)4]·C6H6, have been prepared in powder form and characterized by FT-IR spectroscopy, Raman spectroscopy, X-ray diffraction, thermal analyses and elemental analyses. Vibrational assignments are proposed for the bands of the host lattice and guest molecule. It is shown that the spectra are consistent with a proposed crystal structure for these compounds derived from X-ray diffraction measurements. The C, H, N, Cd and Ni analyses were carried out for all the compounds. Thermal behaviors of these compounds are followed using TG and DTA techniques. The FT-IR, Raman spectroscopic, XRD, thermal and elemental analyses results propose that these compounds are similar in structure to the Hofmann-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)4}, formed from Ni(CN)4 anions coordinated to the bridging 2,3- or 2,5-dimethylpyrazine molecules bound directly to the cadmium. The cadmium atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer.  相似文献   

7.
《Vibrational Spectroscopy》2001,25(2):205-211
IR spectra of M(C5H11N)2Ni(CN)4·G (M=Co, Ni; G=o-, m- or p-xylene; M=Ni; G=dioxane) are reported. These clathrates are analogues to the previously reported classical Hofmann-type clathrates.  相似文献   

8.
Molecular mechanics calculations were carried out to interpret the observed orientational angle of the benzene molecule enclathrated in the Hofmann-type M(NH3)2Ni(CN)4·2 C6H6 (M = Mn, Ni, Cu, and Cd), Hofmann-en-type Cd(en)Ni(CN)4·2 C6H6 (en = NH2CH2CH2NH2), and Hofmannmea-type(2) Cd(mea)Ni(CN)4·2 C6H6 (mea = NH2CH2CH2OH) clathrates using the van der Waals potential functions in Molecular Mechanics Version 2. The angle is most influenced by the guest-to-guest contact in the interlayer space between the two-dimensionalcatena-[metal(II) tetra--cyanonickelate(II)] networks for the Hofmann-type series. The discrepancy between the calculated and the observed angles in each crystal structure was at largest 3.5°; the structures of Cd(NH3)2Ni(CN)4·2 C6H6 and Cd(en)Ni(CN)4·2 C6H6 have been revised using new data collected by counter-methods.  相似文献   

9.
X-ray photoelectron spectra of the single valence platinum complexes K2[Pt(CN)4] · 3H2O(1),K2[Pt(CN)4]Cl0.3 · n H2O(2) and K2[Pt(CN)4]Cl2 · 3H2O(3) and the mixed valence compound [PtII(C2H5NH2)4]Cl4 · [PtIV (C2H5NH2)4Cl2] · 4H2O(4) have been measured. It is found that one can distinguish clearly between mixed and single valence compounds by electron spectroscopy. The Pt spectrum of (4) is a superposition of a PtII and PtIV spectrum. The chemical shift between (1) and (3) is normal, however (2) shows an anomalous low binding energy for the Pt 4f electrons. The importance of using reliable reference peaks for obtaining absolute binding energies is emphasized.  相似文献   

10.
The infrared and diffuse reflectance spectra in the visible and ultraviolet region of the following compounds have been measured: Ni(CN)2, 2 H2O, Ni(CN)2, 1½ H2O, Ni(CN)2, NH3, ¼ H2O, Ni(CN)2, NH3, R (R = C6H6, C6H5NH2, C6H5OH). The structural units of these compounds are shown to be the square planar [NiC4] and the pseudo-octahedral [NiN4L2]-group (L = H2O, NH3) with Ni-C-N-Ni-bridges. Additional water is present as zeolitic water. The magnetic data give a 1:1 relation of the paramagnetic pseudo-octahedral to the diamagnetic square planar co-ordination polyhedra. The nitrogen of the cyanide ion is close to ammonia in the spectrochemical as well as in the nephelauxetic series, the values of Dq and B being ?1000 and ?900 cm?1 respectively. The absorption bands of the aromatic molecules in the clathrates are shifted towards lower wave numbers compared to the corresponding solution spectra.  相似文献   

11.
The crystal structures of the four title clathrate compounds Cd(NH3)2Cd(CN)4 · 2C6H6,I, Cd(NH3)2Cd(CN)4 · 2C6H5NH2,II, Cd(NH2CH2CH2NH2)Cd(CN)4 · 2 C6H5NH2,III, and Cd(C6H5NH2)2Cd(CN)4 · 0.5C6H5NH2,IV, have been analyzed by single crystal X-ray diffraction methods. CompoundI crystallizes in the monoclinic space groupC2/c,a = 12.063(2),b = 12.174(2),c = 14.621(1) Å,β = 90.976(9)°,Z = 4,R = 0.042 for 2388 reflections;II: monoclinic C2/c,a = 12.1951(9),b = 12.078(1),c = 14.6921(7) Å,β = 93.436(5)°,Z = 4,R = 0.039 for 2374 reflections;III: monoclinicCc,a = 11.027(1),b = 12.0767(9),c = 15.837(1) Å,β = 92.059(9)°,Z = 4,R = 0.041 for 2883 reflections; andIV: monoclinicP21/n,a = 15.169(2),b = 16.019(2),c = 8.866(1) Å,β = 95.73(1)°,Z = 4,R = 0.052 for 3612 reflections. The three-dimensionalcatena-[diamminecadmium(II) tetra-μ-cyanocadmate(II)] hosts ofI andII are substantially isostructural to that of the already known Hofmann-Td-type Cd(NH3)2Hg(CN)4 · 2C6H6. The three-dimensional en-Td-typecatena-[catena-μ-ethylenediaminecadmium(II) tetra-μ-cyanocadmate(II)] host ofIII, reinforced by the catena-μ-en linking between the octahedral Cd atoms, accommodates the aniline as the guest with a monoclinic distortion from the tetragonal symmetry of the previously reported en-Td-type benzene clathrate. InIV dual behavior of aniline, one as the unidentate ligand in the three-dimensional host and the other as the guest in the cage-like cavity, has been demonstrated.  相似文献   

12.
Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H2O) and semicarbazone (HL′·H2O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX2·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO3; HL = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0–3; Solv = H2O, CH3OH], CuX2·HL·nH2O [M = Ni, Cu; n = 0, 1], ML2·nH2O and ML′·nH2O [M = Co, Ni, Zn; HL′ = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0–3]. In the presence of amines (A = C5H5N, 2-CH3C5H4N, 3-CH3C5H4N, and 4-CH3C5H4N) these reactions yield the complexes Cu(A)LCl·CH3OH and M(A)LX·nH2O [M = Cu, Ni; X = Cl, NO3; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).  相似文献   

13.
The clathrates Cd(NH3)2 Ni(CN)4·2C6H6 (1) and Cd(en) Ni(CN)4·2C6H6 (2) have been studied as separative materials for the separation of mixtures of alkanes, of benzene and its derivatives, and of the chloroderivatives of methane and pyridine.By identifying the chromatographically active solid form we could observe on the basis of the IR spectra and the thermal analysis that the ethylalcohol after contact with clathrate (1) substituted one mole of benzene. Clathrate (2) was not affected by the action of ethylalcohol. The facts agree with the interactions existing between the tetracyanocomplexes and the sorbates.  相似文献   

14.
In this study, synthesis of two new heteronuclear tetracyanonickelate(II) clathrates based on 4-aminopyridine (4AP) and guest water (H2O) molecule and investigation of their structural properties were reported. These clathrates were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Examining the elemental and spectral data of these clathrates, it was observed that the formulas [Zn(II)(4AP)2Ni(µ-CN)2(CN)2]·6H2O and [Cu(II)(4AP)4Ni(µ-CN)2(CN)2]·H2O were defined their structures. General information about the structural properties of these clathrates in single crystal form has been obtained by considering the changes in the characteristic peaks of the cyanide group and the 4AP that formed them. The thermal behaviors of these clathrates were obtained by examining the temperature-dependent changes of their masses. The magnetic susceptibilities of these clathrates in single crystal form were measured with a Gouy balance. According to the data obtained using SC-XRD technique, the heterometallic [Zn(II)(4AP)2Ni(µ-CN)2(CN)2]·6H2O compound has Cmcm and the heterometallic [Cu(II)(4AP)4Ni(µ-CN)2(CN)2]·H2O compound has crystal structures in the C2 / c space group.  相似文献   

15.
Zusammenfassung Durch Ersetzung des Cadmiums im Clathrat Cden[Ni(CN)4]·2C6H6 wurden drei Verbindungen des TypsM(en) m[Ni(CN)4nC6H6 (M 2+=Ni, Cu, Zn;m=2–3;n=0.14–0.28) hergestellt und charakterisiert.
Synthesis of ethylendiamine-(metal II)-tetracyanoniccolate dibenzene clathrate compounds
Replacing cadmium ion in Cden[Ni(CN)4]·2C6H6 clathrate compound three compounds ofM(en) m[Ni(CN)4nC6H6 type (M 2+=Ni, Cu, Zn;m=2–3;n=0.14–0.28) were prepared and characterized.
  相似文献   

16.
The solubility of components in the system Mg(ClO3)2-2NH2C2H4OH · H3C6H5O7-H2O was studied from the complete freezing temperature ?59.4°C to 20.0°C. A polythermal solubility diagram was constructed, in which the crystallization fields were determined for ice, Mg(ClO3)2 · 16H2O, Mg(ClO3)2 · 12H2O, Mg(ClO3)2 · 6H2O, 2NH2C2H4OH · H3C6H5O7 · H2O, 2NH2C2H4OH · H3C6H5O7, and two new compounds, [(HOC(CH2COOH)2COO)2Mg · 2H2O] and [HOC(CH2COO)2MgCOOH · 2H2O], which were identified by chemical and physicochemical analysis methods.  相似文献   

17.
The thermal behaviour of three coordination compounds, potential precursors of nickel ferrite [Fe2Ni(C4H4O5)2.5(OH)2]NO3·5H2O,[Fe2Ni(C4H8O3N2)4](NO3)8·24H2O and (NH4)[Fe2Ni(C4H4O5)3(OH)3]·3H2O has been investigated to evaluate their suitability as precursors for nickel ferrite. For a complete and reliable assignment of the thermal transformations, the isolable solid intermediates and end products were characterized by IR, X-ray diffraction and Mössbauer investigations. A decomposition scheme is proposed.  相似文献   

18.
IR spectra of Mn(NH3)2M(CN)4·2C6H6 (M=Cd or Hg), and IR and Raman spectra of Cd(NH3)2M(CN)4·2C6H6 (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.  相似文献   

19.
The results of an IR spectroscopie study are presented for six new dianiline metal tetracyanometalate complexes, M(an)2M'(CN)4 (M = Mn, Fe, Co or Cu and M'= Ni; M = Ni or Cd and M' = Pt; an = aniline). Their structure consists of polymeric layers of (M-M'(CN)4)∞ with the aniline molecules bound directly to metal (M). For these series of isomorphous complexes there is a correlation between the shifts of some aniline bands on coordination and the strength of metal-nitrogen bonding measured by the v(M-N) value. Low temperature (83 K) data are also reported and it is noted that whilst the aniline ring and CH mode frequencies are virtually insensitive to temperature, the NH2 wagging, NH2 rocking and the metal-ligand stretching v(M-N) frequencies increase with decreasing temperature, whilst the v(NH2) modes decrease with decreasing temperature. The vibrational frequencies of the M'(CN)4 group are also temperature dependent and increase in value upon cooling the sample to 83 K. The changes are thought to be due to a slight contraction in the cavity size with decreasing temperature. The relationship between these complexes and Hofmann-type aniline clathrates, M(NH3)2M'(CN)4 · 2 an, is indicated.  相似文献   

20.
Interaction of the tetrahedral chalcocyanide cluster anionic complexes of Re, K4[Re4Q4(CN)12] (Q=S, Se, Te), with Ni2+ cationic complexes with polydentate amines, such as ethylenediamine (En), diethylenetriamine (Dien), or triethylenetetraamine (Trien) was used to synthesize six novel complexes: [Ni(NH3)4(En)][{Ni(NH3)(En)2}Re4Te4(CN)12] · 2H2O, [{Ni(En)2}2Re4Se4(CN)12] · 3.5H2O, [Ni(NH3)3(Dien)]2[Re4Se4(CN)12] · 5.5H2O, [{Ni(NH3)2(Dien)}2Re4Te4(CN)12] · 2.5H2O. [Ni(NH3)2(Trien)][{Ni(NH3)(Trien)}Re4Se4(CN)12] · 2.5H2O, [{Ni(Trien)}2Re4S4(CN)12] · 3H2O. The complexes were studied by single-crystal X-ray diffraction analysis.  相似文献   

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