Metal-solvent cluster ions

A higher level of size and morphology control in the incipient semiconductors has been accomplished in reversed micelles prepared from cadmium AOT [614] and from mixtures of cadmium AOT and sodium AOT [615] or, alternatively, by arresting particle growth by surface derivatization [592, 621, 622]. Indeed, surface derivatization of semiconductor clusters was first reported for particles in reversed micelles [621] the reversed micelles act to confine precursor ions and to control the growth of the semiconductor particles. Conditions are typically arranged so that, initially, there is no more than one metal ion (say Cd2+) per water pool. Addition of a heptane solution of bis(trimethylsilyl) selenium resulted in the formation of size-quantized metal selenide particles (say CdSe) in the reversed micelles. This solution could be evaporated to dryness and the resultant particles could be reconstituted in a hydrocarbon solvent Alternatively, addition of metal (say Cd2+) ions to the reversed-micelle-entrapped metal selenide particles, followed by the addition of alkyl(trimethylsilyl)selenium, RMSiMe3, led to the formation of alkyl-capped... 

Photodissociation of the transition-metal cluster ion VFe provides an indirect measure of the absorption spectrum of the lon. Matrix photolysis of M(Tj -CgH,)2(H)CO and M(n -C,H,)2H2 (M-Nb, Ta) yields the monohydrides M(ti -C5Hs)H, uld irradiation of (ti -C.Hs)2V(CH,)2 results in formation of methane and ethame. The amount of ethaine formed is dependent on the solvent, concentration of substrate, time aind temperature. ... 

Zintl also found that the most convenient way to produce the solutions of the anionic clusters in liquid ammonia is to extract alkali metal/post-transition element alloys in the solvent. However, detailed solid-state characterization of the clusters is very difficult using this technique, since poorly crystalline and often pyrophoric solids are obtained once the solvent is evaporated. These troublesome solids are alkali-metal ammoniates of cluster ions, " of which only [Li(NH3)4]3-[Li2(NH3)2Sb5] -2NH3 seem to have been completely structurally characterized, Furthermore, the ammoniates most often slowly revert back to the alloy upon further loss of ammonia. The last step involves transfer of electrons from the strongly reducing cluster anion back to the alkali-metal ion and thus represents a major synthetic obstacle. 

Ousters adsorbed on the outside surfaces of zeolites can often be easily extracted with neutral solvents or with salt solutions which remove the cluster ions by cation metathesis (ion exchange). Comparison of the infrared spectra of the extracted spedes and those of known spedes helps identify the encaged spedes. When treatment of a sample with such solutions fails to remove sorbed dusters, they are inferred to be trapped within the cages. The inference is supported when the same clusters adsorbed on the surface of a large pored material such as an amorphous metal oxide are removed by extraction. 

An alternative to the formation of neutral metal chelates for solvent extraction is that in which the species of analytical interest associates with oppositely charged ions to form a neutral extractable species.6 Such complexes may form clusters with increasing concentration which are larger than just simple ion pairs, particularly in organic solvents of low dielectric constant. The following types of ion association complexes may be recognised. 

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