Crystal structure general discussion

Up to now, we have discussed mostly model intermetallic compounds with simple crystal structures (generally cubic LI2, B2,. . . ) and containing two metal species. We shall now present briefly some properties of point defects in more exotic systems, of considerable interest the A15 superconductors, transition-metal carbides and nitrides, and III-V semiconductors (e.g. GaAs). 

The most important metals for catalysis are those of the groups VIII and I-B of the periodic system. Three crystal structures are important, face-centered cubic (fee Ni, Cu, Rh, Pd, Ag, Ir, Pt, Au), hexagonally dose-packed (hep Co, Ru, Os) and body-centered cubic (bcc Fe). Figure 5.1 shows the unit cell for each of these structures. Note that the unit cells contain 4, 2, and 6 atoms for the fee, bcc, and hep structure, respectively. Many other structures, however, exist when considering more complex materials such as oxides, sulfides etc, which we shall not treat here. Before discussing the surfaces that the metals expose, we mention a few general properties. 

Although several types of lattices have been described for ionic crystals and metals, it should be remembered that no crystal is perfect. The irregularities or defects in crystal structures are of two general types. The first type consists of defects that occur at specific sites in the lattice, and they are known as point defects. The second type of defect is a more general type that affects larger regions of the crystal. These are the extended defects or dislocations. Point defects will be discussed first. 

Almost all the crystalline materials discussed earlier involve only one molecular species. The ramifications for chemical reactions are thereby limited to intramolecular and homomolecular intermolecular reactions. Clearly the scope of solid-state chemistry would be vastly increased if it were possible to incorporate any desired foreign molecule into the crystal of a given substance. Unfortunately, the mutual solubilities of most pairs of molecules in the solid are severely limited (6), and few well-defined solid solutions or mixed crystals have been studied. Such one-phase systems are characterized by a variable composition and by a more or less random occupation of the crystallographic sites by the two components, and are generally based on the crystal structure of one component (or of both, if they are isomorphous). 

If the local structure formation discussed in this chapter is not specific to bmimX ILs but applies to ILs in general, ILs may not be genuine liquids in the conventional sense. They might be better called nano-structured fluid or crystal liquid. They may form a new meso-phase that is distinct from the liquid... 

There is not sufficient space to discuss all vinylidene complexes which have been reported, for example over 200 crystal structures are listed in the CCDC. Consequently, this article largely concentrates on the chemistry of metal vinylidene complexes which has been described since 1995. Vinylidene complexes are generally available for the metals of Groups 4—9, with several reactions of Group 10 alkynyls being supposed to proceed via intermediate vinylidenes. However, few of the latter compounds have yet been isolated. This chapter contains a summary of various preparative methods available, followed by a survey of stoichiometric reactions of vinylidene-metal complexes. A short section covers several non-catalytic reactions which are considered to proceed via vinylidene complexes. The latter, however, have been neither isolated nor detected under the prevailing conditions. 

Our description of atomic packing leads naturally into crystal structures. While some of the simpler structures are used by metals, these structures can be employed by heteronuclear structures, as well. We have already discussed FCC and HCP, but there are 12 other types of crystal structures, for a total of 14 space lattices or Bravais lattices. These 14 space lattices belong to more general classifications called crystal systems, of which there are seven. 

There are a number of factors that determine crystal size. Probably the two most important are the deposition mechanism (ion-by-ion growth, in general, will result in larger crystal size than the hydroxide mechanism, discussed in detail in Chap. 3) and specific adsorption of anions onto the growing crystal (this can affect both crystal structure and size). 

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