Caesium atoms, reactions

The structure of Helvite, Mn CBeSiOJjS, has been reported. The tetrahedral manganese ii) ions are bonded to one sulphur and three oxygen atoms. M2Mn3S4 (M = Rb or Cs) have been prepared by reactions in the molten state under nitrogen. An X-ray study on the caesium compound showed the manganese and caesium atoms to be arranged in layers separated by layers of sulphur atoms. ... 

Basic zeolites were prepared by in situ formation of caesium oxide by calcination of the parent acetate loaded in an increasing amount up to 26 caesium atoms per unit cell. X-ray diffraction and BET studies are consistent with good crystallinity and site accessibility retainings. CO2 TPD results show homogeneous location of the basic species inside the pores with one caesium oxide per supercage. The results are fairly correlated with the initial rates of the Knoevenagel reaction of benzaldehyde and ethylcyanoacetate. These basic solids provide well-adapted selective microporous catalysts for condensation reaction. 

The reaction between dry phosphine and hydrogen iodide, first described in 1817 by J. J.Houtonde la Billardiere produces phosphonium iodide. The simplest laboratory preparation of this compound is by the hydrolysis of an intimate mixture of diphosphorus tetraiodide and white phosphorus According to X-ray diffraction investigations, phosphonium iodide crystallises in a caesium chloride type lattice 3m,32s). 326) hydrogen atoms... 

We saw in Fig. 6-30 the conversion of ethylene oxide to crown ethers upon reaction with appropriate metal salts, and demonstrated that the hole sizes of the products corresponded to the ionic radius of the template ion. However, lest we become over-confident, it should be pointed out that the major product from the reaction of ethylene oxide with caesium salts (r = 1.67 A) is not the expected 21-crown-7 with a hole size of about 1.7 A) but 18-crown-6 (hole size, 1.4 A) (Fig. 6-34). The reason for this lies in the structure of the complex formed. We have always assumed that the metal ion will try to lie in the middle of the bonding cavity of the macrocycle. There is no real reason why this should be. Caesium could form a complex with 21-crown-7 in which all of the oxygen atoms lie approximately planar with the metal in the centre of the cavity. It is also apparent that caesium could not occupy the middle of the cavity in 18-crown-6. However, a different type of complex can be formed with 18-crown-6, in which a caesium ion is sandwiched bet-... 

The trapped electrons were formed simply by depositing alkali metal atoms on ice or solid alcohols at 77°K. Studies were made of the reactions between sodium or potassium atoms and ice (HgO or D2O), methanol, ethanol, isopropyl alcohol, t-butyl alcohol or dodecanol. The reactions of caesium, rubidium and lithium with ice were also investigated. The deposits were highly coloured and the optical and e.s.r. spectra showed that the electron was no longer associated with the alkali metal ion but had been transferred completely to the solid matrix. 

Surface Superbasic Sites of One-electron Donor Character. - The reaction of alkali metal with anionic vacancies on the oxide surfaces (equation 1) leads to the creation of colour centres of F type. The transfer of one electron from the alkali metal atom to an anionic vacancy is the reason for the formation of these defects. The largest quantities of this type of active centre are obtained by evaporation of the alkali metal onto an oxide surface calcined at about 1023 K, at which temperature the largest quantity of anionic vacancies is formed. Oxide surfaces calcined at such high temperatures contain only a small quantity of OH groups ca. 0.5 OH per 100 for MgO and 0.8 OH per 100 for AI2O3), so their role in the reaction is small and the action of alkali metal leads selectively to the creation of defects of the electron in anionic vacancy type. The evidence for such a reaction mechanism is the occurrence of specific colours in the oxide. Magnesium oxide after deposition by evaporation of sodium, potassium, or a caesium turns blue, alumina after sodium evaporation becomes a navy blue in colour, and silica after sodium evaporation becomes violet-brown in colour. ... 

Where the catalyst is less nucleophilic, e.g. potassium fluoride or solid caesium fluoride, only one fluoride ion is likely to coordinate at all firmly to the silane. The nucleophilic reactant will then also be able to coordinate to the electrophilic silicon atom, itself receiving further activation in the process, and reaction ensues by intramolecular transfer about the hexacoordinate silicon atom as demonstrated in the GTP process. Less nucleophilic substrates such as alkyl halides are unreactive in these circumstances. 

Andrews and co-workers have used the matrix reaction between lithium atoms and some inorganic compounds to produce species of spectroscopic interest. Reaction of lithium with molecular oxygen [301] produces, in addition to the molecule Li02, the molecule LiO and a dimer Li2 02. Reaction with nitric oxide produced a nitroxide compound [302], but analysis of the infrared spectrum indicated that in this compound the lithium atom was bound to the oxygen atom (LiON), rather than to the nitrogen atom (LiNO), as would be expected by analogy with the known compounds HNO and RNO. The matrix deposition of lithium and nitrous oxide [303] leads to the formation of LiO and LijO. The other alkali metals have also been reacted in the same way with nitrous oxide [304]. Potassium, rubidium and caesium all led to the formation of the compounds MO and M2O. No sodium oxides were produced when sodium and nitrous oxide were co-deposited. This is to be compared with the mechanism advanced for the sodium-catalysed gas-phase reaction between N2O and CO, where sodium is assumed to react with N2O, (Section 4, ref. 

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