Coordination, terminology

The mechanism of polymerization of alkenes using Ziegler-Natta-type catalysts is described as a coordination [239] or insertion [240] polymerization process. The coordination terminology assumes that the growing polymer chain is bonded to a transition metal atom and that insertion of the monomer into the carbon-metal bond is preceded by, and presumably activated by, the coordination of the monomer with the transition metal center. Since coordination of the monomer may or may not be a specific feature of these polymerizations, the insertion terminology focuses on the proposal that these reactions involve a stepwise insertion of the monomer into the bond between the transition metal atom and the last carbon atom of the growing chain. It is important to note that the bonding of carbon atoms and transition metals is... 

The group-subgroup relation of the symmetry reduction from diamond to zinc blende is shown in Fig. 18.3. Some comments concerning the terminology have been included. In both structures the atoms have identical coordinates and site symmetries. The unit cell of diamond contains eight C atoms in symmetry-equivalent positions (Wyckoff position 8a). With the symmetry reduction the atomic positions split to two independent positions (4a and 4c) which are occupied in zinc blende by zinc and sulfur atoms. The space groups are translationengleiche the dimensions of the unit cells correspond to each other. The index of the symmetry reduction is 2 exactly half of all symmetry operations is lost. This includes the inversion centers which in diamond are present in the centers of the C-C bonds. 

The vector that the genetic algorithm manipulates is known conventionally as a chromosome or a string we shall use the latter terminology in this chapter. The individual units from which each string is constructed, a single x-, y-, or z-coordinate for an atom in this example, are referred to as genes. 

In the course of conventional vibrational spectroscopic calculations in internal coordinates the following eigenvalue-problem has to be solved for the molecule under consideration (FG-method terminology of Wilson, Decius, and Cross (5)) ... 

Possible elements of chirality in stereospecific polymerizations will be briefly recalled in order to indicate the used terminology. First of all, upon coordination, a prochiral olefin such as propene gives rise to not superpos-able si and re coordinations.22 According to the mechanism described, the isotactic polymer is generated by a large series of insertions of all si- or all re-coordinated monomers, while the syndiotactic polymer would be generated by alternate insertions of si - and re-coordinated monomers. 

The manifold intermediates in homogeneous transition-metal catalysis are certainly metal complexes and therefore show a behaviour like ordinary coordination compounds associations of phosphorus donors open up multifarious additional controls. Both, substrates and P ligands are Lewis bases that we have to consider and that compete at the coordination centers of the metal, leading to competitive, non-competitive or uncompetitive activation or inhibition processes in analogy to the terminology of enzyme chemistry... 

If enantiomers are geometrically equivalent4, then what properties can be used to distinguish between them In the terminology based on mathematics, these are topographic properties i.e.. properties that are altered by reflection or, in other words, properties that have to be described by reference to a coordinate system. Absolute configuration is perhaps the topographic property most often encountered by the synthetic chemist. 

Cesium, chloride (CsCl) structure (Fig. 4-H)- The CsCl structure can be described as interpenetrating simple cubic arrays of Cs+ and CP. Again, the Cs+ and CP positions are fully interchangeable. The structure is sometimes wrongly called body-centered cubic (bcc). The terminology is appropriate only when the shaded and unshaded atoms of Fig. 4.11 are identical, as in Fig. 4.8. In any case, the coordination number is eight for any atom. The unit cell of CsCl contains one net CsCl unit. 

Vacancies were later called coordinately unsaturated sites (cus). This is more in line with terminology used in organometallic chemistry. In view of the present understanding of the nature of the active sites, SBMS or Co(Ni)-Mo-S, the following discussion describes mechanisms in terms of catalysis by organometallic complexes. The references available on this topic are too numerous to mention, and the mechanisms are very well understood. A particularly useful reference is the book by Candlin, Taylor, and Thompson (90), although there are many others that can be consulted. 

Werner s terminology ami symbolism differed in small, relatively unimportant ways from that used today. For example. Wcroer referred lo oxidation -state as primary valence Waiipiviilcnc) and coordination number as secondary valence (Nehemulenz) Also, he wrote formulas as Co J A C1 . instead of [CoiNHjljCllClj... 

Since Dickinson s first determinations, crystal structures of many other complexes of various coordination numbers have been determined. All these investigations and others have provided a complete and direct confirmation of Werner s views to support his indirect configurational proofs obtained during the previous decades by preparation of isomers and resolution of optically active compounds (see Section 1.1.4), and today the terminology and concepts of coordination theory are routinely used in crystallography. 

As noted previously, the classification of stereoisomers preferred by contemporary organic chemists is the enantiomer-diastereomer dichotomy17 and this may be quite conveniently applied to coordination compounds. Thus, complexes (9a) and (9b) are enantiomers, but (9a) and (9c), and (9b) and (9c), are diastereomers. Older terminology might have led to the description of A and B as optical antipodes and to (A+B) and C as geometrical isomers. 

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