Oxidation states elimination

When the radicals have p hydrogens, alkenes are formed by a process in which carbocations are probably bypassed. Instead, the oxidation and the elimination of a proton probably occur in a single step through an alkylcopper species. The oxidation state of copper in such an intermediate is Cu(III). 

The coordination chemistry of SO2 has been extensively studied during the past two decades and at least 9 different bonding modes have been established.These are illustrated schematically in Fig. 15.26 and typical examples are given in Table 15.17.1 It is clear that nearly all the transition-metal complexes involve the metals in oxidation state zero or -bl. Moreover, SO2 in the pyramidal >7 -dusters tends to be reversibly bound (being eliminated when... 

Isoindolines comprise a group of well-characterized and easily synthesized substances, and being at the next stable reduction state below that of isoindoles, they constitute suitable precursors for synthesis of the latter. In principle, either oxidation or elimination from isoindolines should lead to isoindoles however, in view of the susceptibility of isoindoles to further oxidation, elimination has been preferred, and in all cases reported the leaving group has been placed on nitrogen rather than carbon. 

Another means of in situ metal-carbene complex formation in an ionic liquid is the direct oxidative addition of the imidazolium cation to a metal center in a low oxidation state (see Scheme 5.2-2, route b)). Cavell and co-workers have observed oxidative addition on heating 1,3-dimethylimidazolium tetrafluoroborate with Pt(PPli3)4 in refluxing THF [32]. The Pt-carbene complex formed can decompose by reductive elimination. Winterton et al. have also described the formation of a Pt-car-bene complex by oxidative addition of the [EMIM] cation to PtCl2 in a basic [EMIM]C1/A1C13 system (free CP ions present) under ethylene pressure [33]. The formation of a Pt-carbene complex by oxidative addition of the imidazolium cation is displayed in Scheme 5.2-4. 

In recent years, several model complexes have been synthesized and studied to understand the properties of these complexes, for example, the influence of S- or N-ligands or NO-releasing abilities [119]. It is not always easy to determine the electronic character of the NO-ligands in nitrosyliron complexes thus, forms of NO [120], neutral NO, or NO [121] have been postulated depending on each complex. Similarly, it is difficult to determine the oxidation state of Fe therefore, these complexes are categorized in the Enemark-Feltham notation [122], where the number of rf-electrons of Fe is indicated. In studies on the nitrosylation pathway of thiolate complexes, Liaw et al. could show that the nitrosylation of complexes [Fe(SR)4] (R = Ph, Et) led to the formation of air- and light-sensitive mono-nitrosyl complexes [Fe(NO)(SR)3] in which tetrathiolate iron(+3) complexes were reduced to Fe(+2) under formation of (SR)2. Further nitrosylation by NO yields the dinitrosyl complexes [(SR)2Fe(NO)2], while nitrosylation by NO forms the neutral complex [Fe(NO)2(SR)2] and subsequently Roussin s red ester [Fe2(p-SR)2(NO)4] under reductive elimination forming (SR)2. Thus, nitrosylation of biomimetic oxidized- and reduced-form rubredoxin was mimicked [121]. Lip-pard et al. showed that dinuclear Fe-clusters are susceptible to disassembly in the presence of NO [123]. 

Secondary bromides and tosylates react with inversion of stereochemistry, as in the classical SN2 substitution reaction.24 Alkyl iodides, however, lead to racemized product. Aryl and alkenyl halides are reactive, even though the direct displacement mechanism is not feasible. For these halides, the overall mechanism probably consists of two steps an oxidative addition to the metal, after which the oxidation state of the copper is +3, followed by combination of two of the groups from the copper. This process, which is very common for transition metal intermediates, is called reductive elimination. The [R 2Cu] species is linear and the oxidative addition takes place perpendicular to this moiety, generating a T-shaped structure. The reductive elimination occurs between adjacent R and R groups, accounting for the absence of R — R coupling product. 

Johnson and Pilson [229] have described a spectrophotometric molybdenum blue method for the determination of phosphate, arsenate, and arsenite in estuary water and sea water. A reducing reagent is used to lower the oxidation state of any arsenic present to +3, which eliminates any absorbance caused by molybdoarsenate, since arsenite will not form the molybdenum complex. This results in an absorbance value for phosphate only. 

The first step is carbon-metal bond formation via coordination. This process may be followed by one or more steps, leading to transformation of ligands and/or reaction between ligands. In a final step, the metal is removed from the organic moiety. Reactions are catalytic or stoichiometric, depending on whether or not the metal is eliminated in its original oxidation state. The following is a broad classification of these processes. 

Strict geometric requirements have allowed the achievement of asymmetric syntheses (7). Reductive elimination is favored by ligands which stabilize the low oxidation state of the metal (8). 

Silver occurs naturally in several oxidation states, the most common being elemental silver (Ag°) and the monovalent ion (Ag+). Soluble silver salts are, in general, more toxic than insoluble salts. In natural waters, the soluble monovalent species is the form of environmental concern. Sorption is the dominant process that controls silver partitioning in water and its movements in soils and sediments. As discussed later, silver enters the animal body through inhalation, ingestion, mucous membranes, and broken skin. The interspecies differences in the ability of animals to accumulate, retain, and eliminate silver are large. Almost all of the total silver intake is usually... 

Quite often, we find nonsystematic nomenclature used in the literature dealing with organophosphorus compounds. This results in unnecessary confusion, as systematic nomenclature is easy to use and understand. Nomenclature based on the oxidation state of the phosphorus center eliminates the confusion and helps to promote understanding of the chemistry as well as to facilitate communication. Table 1.1 shows structures for tricoordinate and tetracoordinate phosphorus compounds related to oxyacids with their English general names. Also noted are the names for simple esters of the parent acids. They are organized based on oxidation state and the number of bonds of the carbon-phosphorus type. 

Rhodium species in oxidation states I and III are involved in the process. Rhodium-catalyzed hydrogenations generally involve oxidative addition reactions, followed by the reverse process of reductive elimination in the final step. Another common elimination process is the so-called (l-elimination, which accounts for the frequent side reaction of isomerization of alkenes, according to Eq. (1) ... 

Another reaction type to be mentioned in this section deals with oxidative addition/reductive elimination. Such reactions not only involve significant bond formation/bond breakage, but also a change in the oxidation state and coordination number of the metal complex. These effects cause significant volume changes such that large... 

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