Higher oxidation states

C2.8.6(c). This increase occurs far below eitlier transpassive dissolution (oxide film dissolution due to tire fonnation of soluble higher oxidation states (e.g. Cr,0., ... 

Metals in higher oxidation states form halides which are essentially covalent, for example AICI3, SnCl, FeClj when these compounds dissolve in water they do so by a strongly exothermic process. Indeed it is perhaps incorrect to think of this only as a dissolution process, since it is more like a chemical reaction—but to differentiate for a particular substance is not easy, as we shall see. The steps involved in the case of aluminium chloride can be represented as... 

With concentrated nitric acid, selenium and tellurium form only their +4 oxoacids, H2Se03 and H2Te03 respectively, indicating a tendency for the higher oxidation states to become less stable as the atomic number of the element is increased (cf. Group V, Chapter 9). 

Also, in anhydrous conditions, silver reacts with fluorine and forms silver difluoride AgFj and cobalt gives cobalt(III) fluoride, C0F3, these metals showing higher oxidation states than is usual in their simple salts. 

It can be seen that xenon has valencies or oxidation states of 2. 4, 6 and 8 compounds with xenon in higher oxidation states are... 

Some of the oxidation states given above, especially the higher oxidation states (7, 6) and oxidation state 0, are found only when the metal atom or ion has attached to it certain groups or ligands. Indeed the chemistry of the transition elements is so dominated by their tendency to form coordination complexes that this aspect of their behaviour must be considered in some detail. 

As might be expected, these higher oxidation states are found almost exclusively in anionic form, and are produced only under strongly oxidising conditions. 

In the chemistry of nickel, we observe the continuing tendency for the higher oxidation states to decrease in stability along the first transition series unlike cobalt and iron, the -e3 state is rare and relatively unimportant for nickel and the +2 state is the only important one. 

Derivatives in which the substituents are already in a higher oxidation state than alkyl groups can be good precursors of acids. Acids can be prepared by the oxidation of alcohols. 

Ground-state electronic configuration is ls 2s 2p 3s 3p 3i 4s. Manganese compounds are known to exist in oxidation states ranging from —3 to +7 (Table 2). Both the lower and higher oxidation states are stabilized by complex formation. In its lower valence, manganese resembles its first row neighbors chromium and especially iron ia the Periodic Table. Commercially the most important valances are Mn, Mn ", or Mn ". ... 

The preparation of mercuric chloride is identical to the chamber method for mercurous chloride, except that an excess of chlorine is used to ensure complete reaction to the higher oxidation state. Very pure product results from this method. Excess chlorine is absorbed by sodium hydroxide in a tower. 

Like mthenium, amines coordinated to osmium in higher oxidation states such as Os(IV) ate readily deprotonated, as in [Os(en) (NHCH2CH2NH2)] [111614-75-6], This complex is subject to oxidative dehydrogenation to form an imine complex (105). An unusual Os(IV) hydride, [OsH2(en)2] [57345-94-5] has been isolated and characterized. The complexes of aromatic heterocycHc amines such as pyridine, bipytidine, phenanthroline, and terpyridine ate similar to those of mthenium. Examples include [Os(bipy )3 [23648-06-8], [Os(bipy)2acac] [47691-08-7],... 

Silver(II) Compounds. Sdver(II) is stabilized by coordination with nitrogen heterocychc bases, such as pyridine and dipyridyl. These cationic complexes are prepared by the peroxysulfate oxidation of silver(I) solutions in the presence of an excess of the ligand. An extensive review of the higher oxidation states of silver has beenpubhshed (21). 

Because transition metals even in a finely-divided state do not readily combine with CO, various metal salts have been used to synthesize metal carbonyls. Metal salts almost always contain the metal in a higher oxidation state than the resulting carbonyl complex. Therefore, most metal carbonyls result from the reduction of the metal in the starting material. Such a process has been referred to as reductive carbonylation. Although detailed mechanistic studies ate lacking, the process probably proceeds through stepwise reduction of the metal with simultaneous coordination of CO (90). 

Treatment of benzo derivatives with oxidizing agents leads to less predictable results. Thus, substituted 2,1-benzisoxazoles with nitrous acid or with CrOs/AcOH generated a variety of ring-opened products of higher oxidation state, the ratio of which depended on the amount of oxidant. These reactions are illustrated in Scheme 30. 

In all of these oxide phases it is possible that departures from the simple stoichiometric composition occur dirough variation of the charges of some of the cationic species. Furthermore, if a cation is raised to a higher oxidation state, by the addition of oxygen to tire lattice, a conesponding number of vacant cation sites must be formed to compensate tire structure. Thus in nickel oxide NiO, which at stoichiomen ic composition has only Ni + cations, oxidation leads to Ni + ion formation to counterbalance the addition of extra oxide ions. At the same time vacant sites must be added to the cation lattice to retain dre NaCl sUmcture. This balanced process can be described by a normal chemical equation thus... 

Fluoroalkyl selenides are oxidized to higher oxidation states by tert-butyl hypochlorite under the mild conditions [115] (equation 105)... 

Among oxygen containing groups, a higher oxidation state takes precedence over a lower one in deter-rnining the suffix of the substitutive nane. Thus, a compound that contains both an alcohol and an aldehyde function is named as an aldehyde. 

Chalcogen-Nitrogen Compounds with the Chalcogen in Higher Oxidation States... 

In general, metallocarboranes are much less reactive (more stable) than the corresponding metallocenes and they tend to stabilize higher oxidation states of the later transition metals, e.g, [Cu (1,2-C2B9Hii)2]2- and [Cu (l,2-C2B9Hii)2] are known whereas cuprocene... 

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