Halogen complexes oxidation states

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. 

A chain mechanism is proposed for this reaction. The first step is oxidation of a carboxylate ion coordinated to Pb(IV), with formation of alkyl radical, carbon dioxide, and Pb(III). The alkyl radical then abstracts halogen from a Pb(IV) complex, generating a Pb(IIl) species that decomposes to Pb(II) and an alkyl radical. This alkyl radical can continue the chain process. The step involving abstraction of halide from a complex with a change in metal-ion oxidation state is a ligand-transfer type reaction. 

The complexes of ruthenium and osmium in the same oxidation state are generally similar and are, therefore, treated together the structural (Table 1.3) and vibrational data (Table 1.4) have been set out in some detail to demonstrate halogen-dependent trends. 

Comparison with data (mainly obtained from EXAFS measurements) on osmium diarsine complexes (Table 1.14) shows that as the oxidation state increases, osmium—halogen bonds shorten whereas Os-P and Os—As bonds lengthen. Bond shortening is predicted for bonds with ionic character,... 

Attempts to oxidise silver dithiocarbamato complexes with halogens to compounds with the metal in higher oxidation states obviously failed. By addition of iodine to a solution of [Ag(Bu2 fc)]g in CHQ3, an insoluble product is formed with the composition rjA% S> X2dtc) 141). With other alkyl groups similar complexes are obtained. Investigations about the nature of this type of compounds are in progress. 

Oxidation of these complexes with halogen results in the oxidation of the ligand, yielding a thiuram disulfide complex X2M(R4tds), leaving the oxidation state of the metal unchanged (99,100,161). 

Halide addition to a cationic carbyne complex, [L M=CR]+, or halogen oxidation of a low oxidation state carbyne complex are both potential routes to monohalocarbene species. Examples of the first process are well known for carbyne complexes from Groups 6 and 7 of the periodic table (120), e.g.,... 

Like all controlled radical polymerization processes, ATRP relies on a rapid equilibration between a very small concentration of active radical sites and a much larger concentration of dormant species, in order to reduce the potential for bimolecular termination (Scheme 3). The radicals are generated via a reversible process catalyzed by a transition metal complex with a suitable redox manifold. An organic initiator (many initiators have been used but halides are the most common), homolytically transfers its halogen atom to the metal center, thereby raising its oxidation state. The radical species thus formed may then undergo addition to one or more vinyl monomer units before the halide is transferred back from the metal. The reader is directed to several comprehensive reviews of this field for more detailed information. 

All the remaining halogens have unfilled d orbitals available and the covalency of the element can be expanded. Compounds and complex ions are formed both with other halogens and with oxygen in which the halogen can achieve a formal oxidation state as high as + 7. for example chlorine has formal oxidation states of +1 in the chlorate(I) anion CIO + 5 in the chlorate(V) anion CIO 3, and + 7 in the chlorate(VII) anion CIO4. ... 

Furthermore, chemical oxidation of [Mo(CO)6] with organic molecules containing acidic hydrogen gives rise to molybdenum species in the +2, -i-3 and +A oxidation states. Higher oxidation states (r-5 and -i-6) have been observed when halogens directly oxidize [Mo(CO)6], A Mo tetranuclear complex has been obtained when hydrochloric acid reacts with the tri-p-hydroxy-dimolybdenum complex, as shown in Equation 9.2 ... 

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