High-oxidation state

Oxygen bonds covalently to many non-metals, and in many oxides, both with metals and non-metals, the other element achieves a high oxidation state, for example... 

This ability to bring out high oxidation states is exhibited also by fluorine it is to be attributed to the high electronegativities of oxygen and fluorine.)... 

An important reason for low coordination of iodide ions is that high coordination implies a high oxidation state of the central atom, which often (but not always) means high oxidising power— and this means oxidation of the easily oxidised iodide ligands. Thus the nonexistence of, for example, phosphorus(V) pentaiodide is to be explained by the oxidation of the iodide ligands and reduction of phosphorus to the -(-3 state, giving only PI3, not PI5. 

Chlorine reacts with most elements, both metals and non-metals except carbon, oxygen and nitrogen, forming chlorides. Sometimes the reaction is catalysed by a trace of water (such as in the case of copper and zinc). If the element attacked exhibits several oxidation states, chlorine, like fluorine, forms compounds of high oxidation state, for example iron forms iron(III) chloride and tin forms tin(IV) chloride. Phosphorus, however, forms first the trichloride, PCI3, and (if excess chlorine is present) the pentachloride PCI5. 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

Halogens can act as ligands and are commonly found in complex ions the ability of fluorine to form stable complex ions with elements in high oxidation states has already been discussed (p. 316). However, the chlorides of silver, lead(Il) and mercury(l) are worthy of note. These chlorides are insoluble in water and used as a test for the metal, but all dissolve in concentrated hydrochloric acid when the complex chlorides are produced, i.e. [AgCl2] , [PbC ] and [Hg Clj]", in the latter case the mercury(I) chloride having also disproportionated. 

Vigorous oxidation leads to the formation of a carboxylic acid but a number of meth ods permit us to stop the oxidation at the intermediate aldehyde stage The reagents most commonly used for oxidizing alcohols are based on high oxidation state transition met als particularly chromium(VI)... 

This reaction is cataly2ed in solution by complexes of tungsten, molybdenum, or rhenium in high oxidation states, eg, Re ". Examples of active catalysts are... 

The performance of many metal-ion catalysts can be enhanced by doping with cesium compounds. This is a result both of the low ionization potential of cesium and its abiUty to stabilize high oxidation states of transition-metal oxo anions (50). Catalyst doping is one of the principal commercial uses of cesium. Cesium is a more powerflil oxidant than potassium, which it can replace. The amount of replacement is often a matter of economic benefit. Cesium-doped catalysts are used for the production of styrene monomer from ethyl benzene at metal oxide contacts or from toluene and methanol as Cs-exchanged zeofltes ethylene oxide ammonoxidation, acrolein (methacrolein) acryflc acid (methacrylic acid) methyl methacrylate monomer methanol phthahc anhydride anthraquinone various olefins chlorinations in low pressure ammonia synthesis and in the conversion of SO2 to SO in sulfuric acid production. 

Smectite [12199-37-0] from an oxidized outcrop is stained light blue by a dilute solution of benzidine hydrochloride. The color does not arise from smectite specifically, but from reaction of a high oxidation state of elements such as Fe " and Mn " (46)46. 

The known halides of vanadium, niobium and tantalum, are listed in Table 22.6. These are illustrative of the trends within this group which have already been alluded to. Vanadium(V) is only represented at present by the fluoride, and even vanadium(IV) does not form the iodide, though all the halides of vanadium(III) and vanadium(II) are known. Niobium and tantalum, on the other hand, form all the halides in the high oxidation state, and are in fact unique (apart only from protactinium) in forming pentaiodides. However in the -t-4 state, tantalum fails to form a fluoride and neither metal produces a trifluoride. In still lower oxidation states, niobium and tantalum give a number of (frequently nonstoichiometric) cluster compounds which can be considered to involve fragments of the metal lattice. 

The highest halide of each metal is of course a fluoride Rep7 (the only thermally stable heptahalide of a transition metal), TcFg, and MnF4. This again indicates the diminished ability of manganese to attain high oxidation states when compared not only to Tc and Re but also to... 

These anions are remarkable not only for the low coordination number but also for the low oxidation state of the metals in combination with oxygen which is more commonly to be found stabilizing high oxidation states. 

The production of tubular positive plates is in principle similar to that of pasted plates. A number of manufacturers use the same gray oxide as the basic filling substance. Sometimes the share or red lead or minium (Pb304) is increased above 25 or even to 100wt.%. The latter is more economic when the manufacturer runs his own minium plant then the expense of the chemical oxidation of lead oxide (PbO) to minium (Pb304) may be compensated by reduced formation cost. Furthermore, curing is not required, because of the high oxidation state, and the battery starts with full capacity when formed. 

High oxidation states are accessible a f-butylimide of ruthenium(VI) can be made by oxidative deprotonation... 

With ethylenediamine, high oxidation states become a possibility (Figure 1.57), sometimes involving a deprotonated ligand (see also section 1.12.1) [148],... 

There is a vigorously expanding chemistry of compounds of ruthenium and osmium in high oxidation states [3, 4, 11, 12], particularly of dioxo and nitrido compounds, though recently some striking developments have taken place in imide chemistry. 

Organic imide ligands have also been used to stabilize high oxidation states. The best example of this is the osmium(VIII) compound Os(NBul)4, which has a distorted tetrahedral OsN4 core (N—Os—N 104.6-111.9° Os—N 1.750 A) [194],... 

Ruthenium and osmium form some remarkably stable alkyls and aryls compounds, often in unusually high oxidation states. 

For many years, the chemistry of silver and gold was believed to be more similar than is now known to be the case [1-10]. In the Cu-Ag-Au triad, the stability of oxidation states does not follow the usual trend of increasingly stable high oxidation state on descending the group for copper, the +2 state is the most important, for silver it is the +1 state and, though oxidation states between -1 and +7 are claimed, for gold it is the +1 and +3 states that dominate its chemistry. The types of compound are summarized in Table 4.1. 

Schrock-type carbenes are nucleophilic alkylidene complexes formed by coordination of strong donor ligands such as alkyl or cyclopentadienyl with no 7T-acceptor ligand to metals in high oxidation states. The nucleophilic carbene complexes show Wittig s ylide-type reactivity and it has been discussed whether the structures may be considered as ylides. A tantalum Schrock-type carbene complex was synthesized by deprotonation of a metal alkyl group [38] (Scheme 7). 

A decade after Fischer s synthesis of [(CO)5W=C(CH3)(OCH3)] the first example of another class of transition metal carbene complexes was introduced by Schrock, which subsequently have been named after him. His synthesis of [((CH3)3CCH2)3Ta=CHC(CH3)3] [11] was described above and unlike the Fischer-type carbenes it did not have a stabilizing substituent at the carbene ligand, which leads to a completely different behaviour of these complexes compared to the Fischer-type complexes. While the reactions of Fischer-type carbenes can be described as electrophilic, Schrock-type carbene complexes (or transition metal alkylidenes) show nucleophilicity. Also the oxidation state of the metal is generally different, as Schrock-type carbene complexes usually consist of a transition metal in a high oxidation state. 

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