Oxidation states, low

Metal derivatives of terminal alkynes, RC2H. Transition metals form complex acetylides (e.g. (M(C = CR) ]- ) often containing the metal in low oxidation states. 

Most metal carbonyls are synthesized in nonaqueous media. Reactive metals, such as sodium (85), magnesium (105), zinc (106), and aluminum (107,108), are usually used as reducing agents. Solvents that stabilize low oxidation states of metals and act as electron-transfer agents are commonly employed. These include diethyl ether, tetrahydrofiiran, and 2-methoxyethyl ether (diglyme). 

Low Oxidation State Chromium Compounds. Cr(0) compounds are TT-bonded complexes that require electron-rich donor species such as CO and C H to stabilize the low oxidation state. A direct synthesis of Cr(CO)g, from the metal and CO, is not possible. Normally, the preparation requires an anhydrous Cr(III) salt, a reducing agent, an arene compound, carbon monoxide that may or may not be under high pressure, and an inert atmosphere (see Carbonyls). 

Acute and Chronic Toxicity. Although chromium displays nine oxidation states, the low oxidation state compounds, -II to I, all require Special conditions for existence and have very short lifetimes in a normal environment. This is also tme for most organ ochromium compounds, ie, compounds containing Cr—C bonds. Chromium compounds that exhibit stabiUty under the usual ambient conditions are limited to oxidation states II, III, IV, V, and VI. Only Cr(III) and Cr(VI) compounds are produced in large quantities and are accessible to most of the population. Therefore, the toxicology of chromium compounds has been historically limited to these two states, and virtually all of the available information is about compounds of Cr(III) and/or Cr(VI) (59,104). However, there is some indication that Cr(V) may play a role in chromium toxicity (59,105—107). Reference 104 provides an overview and summary of the environmental, biological, and medical effects of chromium and chromium compounds as of the late 1980s. 

Oxidation—Reduction. Redox or oxidation—reduction reactions are often governed by the hard—soft base rule. For example, a metal in a low oxidation state (relatively soft) can be oxidized more easily if surrounded by hard ligands or a hard solvent. Metals tend toward hard-acid behavior on oxidation. Redox rates are often limited by substitution rates of the reactant so that direct electron transfer can occur (16). If substitution is very slow, an outer sphere or tunneling reaction may occur. One-electron transfers are normally favored over multielectron processes, especially when three or more species must aggregate prior to reaction. However, oxidative addition... 

Transition metal complexes can be reduced to unusually low oxidation states either with or without bond cleavage, e.g. ... 

The use of liquid NH3 to prepare compounds of elements in unusual (low) oxidation states is exemplified by the successive reduction of K2[Ni(CN)4] with Na/Hg in the presence of an excess of CN the dark-red dimeric Ni complex K4[Ni2(CN)6] is first formed and this can be further reduced to the yellow Ni° complex K4[Ni(CN)4]. The corresponding complexes [Pd(CN)4]" and [Pt(CN)4]" can be prepared similarly, though there is no evidence in these latter systems for the formation of the M dimer. A ditertiaiyphosphine complex of Pd° has also been prepared ... 

In all the cluster compounds discussed above there are sufficient electrons to form 2-centre 2-electron bonds between each pair of adjacent atoms. Such is not the case, however, for the cationic bismuth species now to be discussed and these must be considered as electron deficient . The unparalleled ability of Bi/BiCb to form numerous low oxidation-state compounds in the presence of suitable complex anions has already been mentioned (p. 564) and the cationic species shown in Table 13.12 have been unequivocally identified. 

The versatility of cyanide and bipyridyl ligands has been used to stabilize low oxidation states. By using potassium in liquid ammonia, K3Ti (CN)6 is reduced to K2Ti (CN)4 and TiBt3 - - KCN to K4Ti°(CN)4. With ZrBt3 and M CN (M = K, Rb) in liquid ammonia, ammonolysis occurs and zerovalent Zr is produced ... 

The chemistry of technetium(II) and rhenium(II) is meagre and mainly confined to arsine and phosphine complexes. The best known of these are [MCl2(diars)2], obtained by reduction with hypophosphite and Sn respectively from the corresponding Tc and Re complexes, and in which the low oxidation state is presumably stabilized by n donation to the ligands. This oxidation state, however, is really best typified by manganese for which it is the most thoroughly studied and, in aqueous solution, by far the most... 

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 mechanism by which this low oxidation state is stabilized for this triad has been the subject of some debate. That it is not straightforward is clear from the fact that, in contrast to nickel, palladium and platinum require the presence of phosphines for the formation of stable carbonyls. For most transition metals the TT-acceptor properties of the ligand are thought to be of considerable importance and there is... 

Aetinide ehaleogenides ean be obtained for instanee by reaetion of the elements, and thermal stability deereases S > Se > Te. Those of a given aetinide differ from those of another in mueh the same way as do the oxides. Nonstoiehiometry is again prevalent and, where the aetinide appears to have an uneharaeteristieally low oxidation state, semimetallie behaviour is usually observed. 

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. 

Since n bonding is believed to be more important in low oxidation states, as d orbitals contract with increasing oxidation state leading to poorer dw-pw overlap, this would not be expected on the basis of a 7r-bonding mechanism. Similarly, one can compare /(Pt-P) for pairs of isomers in the +2 and +4 states in a planar platinum(II) complex, the platinum 6s orbital is shared by four ligands whereas in an octahedral platinum(IV) complex it is shared by six ligands. Therefore, the 6s character is expected to be only 2/3 as much in the platinum(IV) complexes, correlating well with the 7(Pt-P) values, which can be taken to be a measure of the a-character in the bond. 

Two possible reasons may be noted by which just the coordinatively insufficient ions of the low oxidation state are necessary to provide the catalytic activity in olefin polymerization. First, the formation of the transition metal-carbon bond in the case of one-component catalysts seems to be realized through the oxidative addition of olefin to the transition metal ion that should possess the ability for a concurrent increase of degree of oxidation and coordination number (177). Second, a strong enough interaction of the monomer with the propagation center resulting in monomer activation is possible by 7r-back-donation of electrons into the antibonding orbitals of olefin that may take place only with the participation of low-valency ions of the transition metal in the formation of intermediate 71-complexes. 

In the course of this development, knowledge about low valent (in the sense of formal low oxidation states) reactive intermediates has significantly increased [26-30]. On the basis of numerous direct observations of silylenes (silanediyles), e.g., by matrix isolation techniques, the physical data and reactivities of these intermediates are now precisely known [31], The number of kinetic studies and theoretical articles on reactive intermediates of silicon is still continuously growing... 

The chemistry of silicon in very low oxidation states is one of the most fascinating research areas, which can be located between molecular compounds of silicon and elemental (perhaps amorphous) silicon [190-194]. Most interesting results have recently been obtained by structural investigations of siliddes in Zintl phases. However, compounds of silicon with negative oxidation states and very low coordination numbers of 1, 2, and 3 are so far only known in the composite of a crystal lattice. 

Ligand induced redox reactions of low oxidation state rhenium halides and related systems in non-aqueous solvents. R. A. Walton, Prog. Inorg. Chem., 1976, 21, 105-127 181). 

Metal halides in low oxidation states. J. D. Corbett, Prep. Inorg. React., 1966,3,1-33 (141). 

Compounds that contain the element in a low oxidation state, such as Cr2+, are often good reducing agents ... 

The range of oxidation states of a d-block element increases toward the center of the block. Compounds in which the d-block element has a high oxidation state tend to be oxidizing those in which it has a low oxidation state tend to be reducing. The acidic character of oxides increases with the oxidation state of the element. 

Low oxidation states - An important characteristic of transition metal chemistry is the formation of compounds with low (often zero or negative) oxidation states. This has little parallel outside the transition elements. Such complexes are frequently associated with ligands like carbon monoxide or alkenes. Compounds analogous to Fe(CO)s, [Ni(cod)2] (cod = 1,4-cyclooctadiene) or [Pt(PPh3]3] are very rarely encountered outside the transition-metal block. The study of the low oxidation compounds is included within organometallic chemistry. We comment about the nature of the bonding in such compounds in Chapter 6. 

The species discussed so far belong to the class we might label Werner-type complexes. We use this description to differentiate from carbonyl-type or other low oxidation state complexes. We stay with Werner-type complexes exclusively until Chapter 6. The radial waveforms for 3d, A-s and Ap orbitals of the metals in such... 

In low oxidation states, transition metals possess filled or partly filled d shells. The Dewar-Chatt-Duncanson model envisages some of that electron density in (local) d (e.g. d., d y) orbitals being donated into the empty n orbitals of the carbon monoxide ... 

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