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1.
The double cyanides of nickel and platinum form structures capable of enclosing also phenol, for example, as guest molecule. Such clathrates are Ni(NH3)2Pt(CN)4 2 C6H5OH and Ni(en)2Pt(CN)4 · 0.14 C6H5OH. In the case of the tetracyano complexes, different thermal stabilities of their clathrate compounds could be achieved by alteration of the constituents of the cage structure and also of the guest molecules. According to the thermal behaviour, the clathrates may be divided into two groups: those which release the guest molecules in the first step of thermal decomposition (Ni(NH3)2Pt(CN)4· 2 C6H5OH), and those which lose the guest component only after partial destruction of the host cage (Ni(en)2Pt(CN)4 · 0.14 C6H5OH). The temperature ranges of loss of the guest component may determine the interval for their use in sorptive experiments. The temperature range for release of phenol from Ni(NH3)2Pt(CN)4 · · 2 C6H5OH is 55–244°, and from Ni(en)2Pt(CN)4 · 0.14 C6H5OH is 139–284°. The model host molecules NiPt(CN)4 · 6 H2O and Ni(en)3Pt(CN)4 · 3 H2O were also studied by thermal analysis.  相似文献   

2.
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   

3.
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   

4.
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   

5.
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   

6.
Tetracyanocomplexes can be non-stoichiometric in three different ways: 1. The preparation of complexes such as M(NH3)2M'(CN)4.nG and M(en)m H'(CN)4.nG can result in a non-stoichiometric product i.e. n is non-integer (refs. 1 and 2). 2. Heating a fully stoichiometric compound such as M(NH3)2M'(CN)4.2G, can result in the loss of some of the guest molecules (ref. 3). 3. A stoichiometric or non-stoichiometric compound can absorb an aromatic molecule of the appropriate size (refs. 4–6) when heated in the presence of the molecule.  相似文献   

7.
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   

8.
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   

9.
Summary The new complex double saltscw-[Co(NH3)(en)2(H2O)]2 [M(CN)4]3 (en = ethylenediamine; M = Ni, Pd or Pt),cis-[Co(NH3(en)2(H2O)]2[FeNO(CN)5]3 andcis-[Co(NH3)(en)2(H2O)][Co(CN)6] have been synthesized and by anation in the solid state the corresponding new dinuclear complexes with a cyano bridgecis- ortrans-[(NH3)(en)2Co-NC-M(CN)3]2 [M(CN)4] (M = Ni, Pd or Pt);cis-, trans-[(NH3)(en)2Co-NC-FeNO(CN)4]2[FeNO(CN)5] andcis-[(NH3)(en)2Co-NC-Co(CN)5 have been prepared. The complexes have been characterized by chemical analysis, t.g. measurements, and by i.r. and electronic spectroscopy. With [Ni(CN)4][2– and [Co(CN)in]6 3– only thecis-isomer is produced; with [Pd(CN)4]2–, [Pt(CN)4]2– and [FeNO(CN)5]2– thetrans- isomer is the dominant species. The dinuclear complex derived from [Pt(CN)4]2– shows strong Pt-Pt interactions both in the solid state and in solution.  相似文献   

10.
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   

11.
Two new complexes containing M(II) ammine cations (M = Ni, Cd) and octahedral rhenium(III) thiocyanoammine and thiocyanohydroxoammine cluster anions, [Ni(NH3)6][Re6S8(CN)4(NH3)2]?2H2O (1) and [Cd(NH3)6][{Cd(NH3)5}{Re6S8(CN)4(OH)(NH3)}]2?5H2O (2), have been synthesized by hydrothermal reactions starting from Cs1.83K2.17[Re6S8(CN)4(OH)2]?2H2O. The compounds were structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis, energy dispersive spectroscopy, and IR spectroscopy. Both compounds adopt monoclinic crystal structures composed from discrete ionic species which are held together by multiple hydrogen bonds between CN, OH, and NH3 ligands and lattice water. 2 consists of {Cd(NH3)5}2+ attached to the OH group of the [Re6S8(CN)4(OH)(NH3)]3– cluster anion via the Re–OH–Cd linkage.  相似文献   

12.
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   

13.
IR spectra of Mn(en)M(CN)4·2C6H6 (M=Cd or Hg), and IR and Raman spectra of Cd(en)M(CN)4·2C6H6 (M=Cd or Hg) clathrates are reported. The spectral features suggest that the first two compounds are similar in structure to the later two Td-type clathrates.  相似文献   

14.
On the Crystal Structures of the Cyano Complexes [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O, and [Cu(en)2][Ni(CN)4] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH3)6][Fe(CN)6] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH3)6][Co(CN)6] type structure. [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H2O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)2][Ni(CN)4] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.  相似文献   

15.
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   

16.
The compounds NiNi(CN)4·3,5H2O and Ni(NH3)2Ni(CN)4·H2O have been studied to examine the possibility of substituting their H2O or NH3 content by D2O. Contact with D2O was performed after heating the compounds to several temperatures. Depending on the degree of decomposition of the original compounds different ranges of substitution were possible. In such manner the compounds NiNi(CN)4·3,5D2O, NiNi(CN)4·5D2O, Ni(NH3)2Ni(CN)4·D2O, and Ni(D2O)2Ni(CN)4·D2O were prepared and thermally they were less stable than the original ones. The substitution by D2O is in agreement with the sorptive properties of the original tetracyanonickelate against different organic compounds using GC, since these could substitute the guest component and sometimes also the ligands during their decomposition.  相似文献   

17.
Synthesis and IR spectra of novel Hofmann-T d -type aniline clathrates, M(NH3)2Zn(CN)4· 2C6H5NH2 (M = Zn or Cd) are reported for the first time. All the vibrational modes of aniline are characterised. The shifts in a (NH2) and s (NH2) reveal hydrogen bonding between the NH2 group of aniline and the cyanide group of the host lattice to be stronger than in Hofmann-type aniline clathrates. However, the out of plane deformation mode of aniline indicates absence of hydrogen bonding between ammonia and the -cloud of the aniline ring. The related aniline clathrates with bridging Cd(CN)4 M(NH3)2Cd(CN)4· 2C6H5NH2 (M=Zn or Cd), exhibit similar behaviour.  相似文献   

18.
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   

19.
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   

20.
Infrared spectra of Mn(NH3)2Zn(CN)4.2C6H6 andMn(ethylenediamine)Zn(CN)4.2C6H6 are reported. The spectral data suggest that these compounds are similar in structure toHofmann-Td-type and the en-Td-type clathrates,respectively. There is good evidence for H-bonding from ammoniaN–H to benzene as a to H-bond.  相似文献   

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