Clathrate compounds of tetracyano complexes of nickel and platinum with phenol

Abstract

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 C6HsOH and Ni(en)2Pt(CN)~ 9 0.14 CeHsOH. 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 C,HsOH), and those which lose the guest component only after partial destruction of the host cage (Ni(en)~Pt(CN)4 9 0.14 C~HsOH) 9 The temperature ranges of loss of the guest component may determine the interval for their use in sorptive experiments 9 The temperature range for release of phenol from Ni(NH3)2Pt(CN)a 9 9 2 C6HsOH is 55--244 ~ and from Ni(en)2Pt(CN)4 9 0.14 C6HsOH is 139-284 ~ The model host molecules NiPt(CN)4 9 6 H~O and Ni(en)3Pt(CN)4 9 3 H20 were also studied by thermal analysis 9The clathrate compounds of tetracyano complexes have been found [11 to exhibit higher thermal stabilities that other clathrate compounds described in the literature. This holds not only for the clathrate compounds themselves, generally written as M(NH3)2M'(CN)4 9 2 G and M(en)mM'(CN)~ " nG, but also for their host molecules the tetracyano complexes [2]. The host molecules have been prepared for a better understanding of the relations between the clathrate compounds, their properties described in the literature and also their behaviour in several sorptive processes [3].The double cyanides form structures capable of enclosing guest components present in the reaction medium during the synthesis of the double cyanide 9 By altering the constituents of the cage structures of the host molecules, we could achieve different thermal stabilities of the resulting clathrate compounds. We used M in the. form of Ni n, Cu u, Cd n and Znn; M' in the form of Ni 1I, Pt u and pdlI; and m = 1, 2 and 3.Equally, the interaction of the cage with the individual types of guest molecules influences the thermal stabilities of the synthesized clathrate compounds. As guest 7 3-. Thermal Anal. 12, 1977

Vibrational Spectroscopic Investigation on Some M(Benzonitrile)2Ni(CN)4 Complexes (M = Ni, Zn, Cd, and Hg)

“…4 or Hg) complexes are given in Table 4. Similar decomposition stages have been observed for other Hofmanntype complexes [30,31] and Hofmann-type clathrates [32][33][34][35].…”

FT-IR spectroscopic study of the Hofmann type clathrates: M(4-Chpy)2 Ni(CN)4·nG (M=Ni or Co; G=1.4-dioxane)

“…Assignments and wavenumbers of the vibrational bands for the guest molecule observed in the infrared spectra of the compounds are given in Table 3 along with the wavenumbers of dioxane in liquid phase [14], through which assignments were carried out.…”