Structural effects Group 1 elements

In this work we present models for the quantitative description of the structural effects of substituents whose first or second atom is silicon, germanium, tin or lead. Silicon has been included in this work because its behavior is analogous to that of the remaining elements of the group and there is much more information available for silicon containing substituents than there is for all of the other elements. There are only two types of substituent we shall consider here. They are ... 

Considering the influence of electronic configurations on crystal structures it may be asked, whether certain structure t5rpes are restricted to fluorine compounds of the transition elements. Apart from the structure types distorted by the Jahn-Teller effect such a limitation is not obvious at all. On the contrary quite a number of structure prototypes are represented by compounds of the main group elements. Bonding thus must be similar in both, main group and transition element fluorides, at least as for the factors that influence crystal structmes. 

The crystal structures adopted by the binary carbides and nitrides are similar to those found in noble metals. The resemblance is not coincidental, and has been explained using Engel-Brewer valence bond theory [5]. Briefly, the main group elements C and N increase the metal s effective s-p electron count, so that structures and chemical properties of the early transition metals resemble those of the Group 8 metals. This idea was first introduced by Levy and Boudart [6] who noted that tungsten carbide had platinum-like properties. 

Molybdenum is in Sub-Group VI A/B of the Periodic Table, and in the second series of transition elements. Transition elements are those which have an incomplete inner orbit in their atomic structure (see Table 3.1), and such an incomplete orbit is less stable than a filled orbit. The result is that the transition elements, and their compounds, show resemblances to each other and peculiarities in comparison with non-transition elements. It is therefore interesting that a number of compounds of other transition elements have been studied for solid lubricant use, and some of them have been found to be very effective, but no-one has yet shown any particular relationship between transition element structures and lubricating performance. The electron orbital assignments for these various elements are shown in Table 3.1. 

The objective of this work is to present models for the quantitative description of structural effects of substituents involving Group 15 elements. It is useful for this purpose to summarize the types of substituents we shall consider here. They include ... 

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