Stoichiometric family

Each electronic state of the given stoichiometric family corresponds to a formal potential energy hypersurface E(K). Clearly, the notions of chemical species, chemical identity, and molecular deformation are dependent on the electronic state. A specific nuclear arrangement that is stable for one electronic state... 

Consider two different subsets of the same space D, or subsets of two dynamic shape spaces D and D of two different stoichiometric families of molecules. One may compare those domains of the two subsets that belong to the same shape group H 2. Since within these domains the nuclear configuration is not fully specified, that is, there exists some configurational freedom within these domains, the above approach provides a description of the dynamic similarity of molecular shapes. We shall return to the problems of dynamic shape similarity in Chapter 6. 

Based on the above neighbor relation, and by direct analogy with the model of ref.[20], we define the point symmetry graph g(M,sym) of the nuclear configuration space M of the given stoichiometric family of chemical species by the following relations ... 

For example, atoms of both the alkaline-earth family (ZAval = 2) and the chalcogen family (ZAval = 6) correspond to FAemp = 2, and their stoichiometric proportionality (or coordination number) to monovalent atoms is therefore commonly two (AH2, ALi2, AF2, etc.). It is a remarkable and characteristic feature of chemical periodicity that the empirical valency FAemp applies both to covalent and to ionic limits of bonding, so that, e.g., the monovalency of lithium (Vuemp = 1) correctly predicts the stoichiometry and coordination number of covalent (e.g., Li2), polar covalent (e.g., LiH), and extreme ionic (e.g., LiF) molecules. Following Musher,132 we can therefore describe hypervalency as referring to cases in which the apparent valency FA exceeds the normal empirical valency (3.184),... 

Notice, moreover, that for a family of binary and complex phases such as the Laves phases (Cu2Mg, MgZn2, Ni2Mg types) an overall number of about 1400 has been estimated. The restriction of the phase concentration to a limited number of stoichiometric ratios is also valid (and, perhaps, more evident) for the ternary phases. We may notice in Fig. 7.2, adapted from a paper by Rodgers and Villars (1993), that seven stoichiometric ratios (1 1 1, 2 1 1, 3 1 1, 4 1 1, 2 2 1, 3 2 1, 4 2 1) are the most prevalent. According to Rodgers and Villars they represent over 80% of all known ternary compounds. 

Katsuki and coworkers have developed a family of salen-metal complexes capable of effecting a C—H oxidation at activated positions. meso-Tetrahydrofurans may be oxidized to the lactol in good yield and excellent enantioselectivity using iodosylbenzene as the stoichiometric oxidant and a Mn-salen complex as catalyst [Eq. (10.45)]. " Meso acylpyrrolidines behave similarly, providing slightly lower enantioselectivities using a similar catalyst [Eq. (10.46)]d ... 

Another approach to preparing enantiomerically pure carboxylic acids and related compounds is via enanhoselective reduction of conjugated double bonds using NAD(P)H-dependent enoate reductases (EREDs EC 1.3.1.X), members of the so-called Old Yellow Enzyme family [44]. EREDs are ubiquitous in nature and their catalytic mechanism is well documented [45]. They contain a catalytic flavin cofactor and a stoichiometric nicotinamide cofactor which must be regenerated (Scheme 6.23). 

Another closely related family of superconductors is represented by the formula TlBa2Can 1Cun02n+3 (n = 1, 2, 3, 4, 5). They contain single layers of T1 and O atoms that separate the perovskite-like Ba-Cu-Ca-O slabs (24)(25)(26)(27) (Figure 6). Distortions in the Tl-O sheets are also found in these compounds (26)(27). Note that if these phases were stoichiometric, copper would always have a formal oxidation state of greater than two. Therefore, the chemical composition of this homologous series allows the existence of holes in the copper-oxygen sheet. 

EuO is an interesting oxide in the rocksalt family (Honig Van Zandt, 1975). It is a ferromagnetic T = 69 K) insulator when pure and stoichiometric. Unlike the M oxides, superexchange interaction in EuO is ferromagnetic because the charge transfer... 

What makes the TTF-TCNQ family distinct from the other salts of TCNQ with cations, such as alkali metals and tetramethylammonium, is that the charge transfer,/ in the TTF-TCNQ family is incomplete (f < 1). TTF-TCNQ members are also different from the TTF-halides in the TTF-halides, where the charge on each halide atom is unity, partial charge transfer (mixed valency) is realized by the formation of nonstoichiometric materials, while in the TTF-TCNQ family, the composition is stoichiometric (1 1), but mixed valence arises because of partial electron-transfer. 

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