Stoichiometric names anions

IR-5.2 Stoichiometric names of elements and binary compounds IR-5.3 Names of ions and radicals IR-5.3.1 General IR-5.3.2 Cations IR-5.3.2.1 General IR-5.3.2.2 Monoatomic cations IR-5.3.2.3 Homopolyatomic cations IR-5.3.2.4 Heteropolyatomic cations IR-5.3.3 Anions IR-5.3.3.1 Overview IR-5.3.3.2 Monoatomic anions IR-5.3.3.3 Homopolyatomic anions IR-5.3.3.4 Heteropolyatomic anions IR-5.4 Generalized stoichiometric names... 

Homopolyatomic anions are named by adding the charge number to the stoichiometric name of the corresponding neutral species, i.e. the element name with the appropriate multiplicative prefix. Again, a radical dot may be added as appropriate. 

It has been well recognized that the hydrolysis of alkoxysilanes and chlorosilanes is effectively catalyzed when fluoride anions are present due to formation of hypercoordinated silicon intermediates.803 More in-depth studies by Bassindale et al. showed that the reaction of PhSi(OEt)3 with stoichiometric amounts of Bu4NF surprisingly yields an encapsulation complex, namely tetrabutylammonium octaphenyloctasilsesquioxane fluoride 830, in which the fluorine atom is situated inside the cubic siloxane cage (Scheme 114). The Si--F distance of average 2.65 A is shorter than the sum of van der Waals radii (3.57 A), which renders the coordination number of the silicon atoms at [4+1]. 

It was found that the intercalation of Cgo fullerene by an alkali metal in stoichiometric ratio (1 1) gives rise to the formation of anion-radical salts, namely, KC50, RbCgg, and CsCgo (Bommeli et al. 1995, Btouet et al. 1996). On slow cooling of the intercalation products, [2 + 2] cycloaddition of the fullerene species that is neighboring a crystal lattice occurs. Linear chain fullerenic polymers are formed. These polymers are stable in air, insoluble in THF, and possess metallic conductivity. They depolymerize only on heating above 320°C. 

Since different reactivity is observed for both the stoichiometric and the catalytic version of the arene-promoted lithiation, different species should be involved in the electron-transfer process from the metal to the organic substrate. It has been well-established that in the case of the stoichiometric version an arene-radical anion [lithium naph-thalenide (LiCioHg) or lithium di-ferf-butylbiphenylide (LiDTBB) for using naphthalene or 4,4 -di-ferf-butylbiphenyl (DTBB) as arenes, respectively] is responsible for the reduction of the substrate, for instance for the transformation of an alkyl halide into an alkyllithium . For the catalytic process, using naphthalene as the arene, an arene-dianion 2 has been proposed which is formed by overreduction of the corresponding radical-anion 1 (Scheme 1). Actually, the dianionic species 2 has been prepared by a completely different approach, namely by double deprotonation of 1,4-dihydronaphthalene, and its X-ray structure determined as its complex with two molecules of N,N,N N tetramethylethylenediamine (TMEDA). ... 

The student may well feel that the need to name inorganic compounds is a relic of the past, when stoichiometric formulae were often uncertain, and that a formula will convey a more concise specification of a substance. This attitude is not without merit, especially where we are dealing with rather complex substances whose systematic names are hopelessly clumsy and lengthy. For example, the important substance rendered as IrCl(CO)(PPh3)2 on the printed page has the systematic name trans-chlorocarbonylbis(triphenylphosphine)iridium(I). Although hundreds of papers have been published on the reactions of this compound and tens of thousands of students have heard of it, the systematic name is rarely used. In speech, and often in print, it is given the trivial name Vaska s compound . In any research laboratory, you may hear talk of Judy s compound , or Ralph s anion . 

Schottky defects, named after W. Schottky, consist of unoccupied anion and cation sites. A stoichiometric crystalline oxide having Schottky disorder alone contains charge-equivalent numbers of anion and cation vacancies. A Frenkel... 

A mechanistically different type of nitrosation was discovered by Keefer and Roller (1973), namely a nitrosation of secondary aliphatic amines with nitrite anions in alkaline solution, catalyzed by aldehydes. Although it is unlikely to be applicable to diazotization, i. e., to primary amines, it will be mentioned here because it is a good example of the fact that, in chemistry, particularly in organic chemistry, for a certain type of reaction, e. g., nitroso-de-protonation (which includes substitution of protons bonded to C, N, O, S, etc., atoms), practically all methods follow the same basic pattern (in the case of nitrosation substitution by an electrophilic nitrosating reagent). The Keefer-Roller nitrosation is apparently different if one looks at the stoichiometric equation (4-8). A careful kinetic investigation (Casado et al., 1981b, 1984 a) on the concentration and pH dependence of this reaction revealed that the nitrite anion and free amine base enter the substitution process and that formaldehyde is a true catalyst, as it is not required in equimolar amounts. 

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