Bonding and physical properties

In limiting this chapter to metal-phosphine complexes, many significant compounds and nitrogen-fixing systems will not be discussed. However, interested readers are referred to a number of relatively recent reviews of the chemistry of nitrogen fixation. " Similarly, adequate descriptions of the bonding and physical properties of the metal dinitrogen complexes have appeared elsewhere and will only be mentioned in this chapter where relevant. 

At present no microscopic theory exists which can answer questions like this, and there are few phenomenological descriptions either. What is badly needed is a common framework which will at least facilitate the development of incisive and informative phenomenological descriptions. I believe that polarizabilities can provide such a framework, and that they can be used to explain trends in chemical bonding and physical properties even when an absolute and rigorous connection is not demonstrated. For this to become so, however, it is necessary to understand the quantum mechanical meaning of polarizabilities in a more profound way than has generally been the case in the past. The story of how little this rather simple subject has been explored theoretically illustrates why it is that our understanding of the properties of materials is still at so primitive a level. 

Clusters are intennediates bridging the properties of the atoms and the bulk. They can be viewed as novel molecules, but different from ordinary molecules, in that they can have various compositions and multiple shapes. Bare clusters are usually quite reactive and unstable against aggregation and have to be studied in vacuum or inert matrices. Interest in clusters comes from a wide range of fields. Clusters are used as models to investigate surface and bulk properties [2]. Since most catalysts are dispersed metal particles [3], isolated clusters provide ideal systems to understand catalytic mechanisms. The versatility of their shapes and compositions make clusters novel molecular systems to extend our concept of chemical bonding, stmcture and dynamics. Stable clusters or passivated clusters can be used as building blocks for new materials or new electronic devices [4] and this aspect has now led to a whole new direction of research into nanoparticles and quantum dots (see chapter C2.17). As the size of electronic devices approaches ever smaller dimensions [5], the new chemical and physical properties of clusters will be relevant to the future of the electronics industry. 

Molecu lar mechari ical force fields use the equation s of classical mech an ics to describe th e poteri tial energy surfaces and physical properties of m olecii Ies. A molecu le is described as a collection of atom slhal in teracl with each other by sim pic an alytical fiiriclions. I h is description is called a force field. One component of a force field is th e eri ergy arisiri g from com pression and stretch in g a bond. 

Castor oil (qv) contains a predominance of ricinoleic acid which has an unusual stmcture inasmuch as a double bond is present in the 9 position while a hydroxyl group occurs in the 12 position. The biochemical origin of ricinoleic acid [141-22-0] in the castor seed arises from enzymatic hydroxylation of oleoyl-CoA in the presence of molecular oxygen. The unusual stmcture of ricinoleic acid affects the solubiUty and physical properties of castor oil. 

Substitution of fluorine for hydrogen in an organic compound has a profound influence on the compound s chemical and physical properties. Several factors that are characteristic of fluorine and that underHe the observed effects are the large electronegativity of fluorine, its small size, the low degree of polarizabiHty of the carbon—fluorine bond and the weak intermolecular forces. These effects are illustrated by the comparisons of properties of fluorocarbons to chlorocarbons and hydrocarbons in Tables 1 and 2. 

Electronic-Grade MMCs. Metal-matrix composites can be tailored to have optimal thermal and physical properties to meet requirements of electronic packaging systems, eg, cotes, substrates, carriers, and housings. A controUed thermal expansion space tmss, ie, one having a high precision dimensional tolerance in space environment, was developed from a carbon fiber (pitch-based)/Al composite. Continuous boron fiber-reinforced aluminum composites made by diffusion bonding have been used as heat sinks in chip carrier multilayer boards. 

Phosphorus compounds exhibit an enormous variety of chemical and physical properties as a result of the wide range ia the oxidation states and coordination numbers for the phosphoms atom. The most commonly encountered phosphoms compounds are the oxide, haUde, sulfide, hydride, nitrogen, metal, and organic derivatives, all of which are of iadustrial importance. The hahde, hydride, and metal derivatives, and to a lesser extent the oxides and sulfides, are reactive iatermediates for forming phosphoms bonds with other elements. Phosphoms-containing compounds represented about 6—7% of the compound hstiugs ia Chemical Abstracts as of 1993 (1). 

Reactions of the Disulfide Group. Besides the thiol end groups, the disulfide bonds also have a marked influence on both the chemical and physical properties of the polysulftde polymers. One of the key reactions of disulfides is nucleophilic attack on sulfur (eq. 4). The order of reactivity for various thiophiles has been reported as (C2H O) P > R, HS , C2H5 S- >C,H,S- >C,H,P,... 

Thermodynamic and physical properties of water vapor, Hquid water, and ice I are given ia Tables 3—5. The extremely high heat of vaporization, relatively low heat of fusion, and the unusual values of the other thermodynamic properties, including melting poiat, boiling poiat, and heat capacity, can be explained by the presence of hydrogen bonding (2,7). 

Theories of molecular stracture attempt to describe the nature of chemical bonding both qualitatively and quantitatively. To be useful to chemists, the bonding theories must provide insight into the properties and reactivity of molecules. The stractural theories and concepts that are most useful in organic chemistry are the subject of this chapter. Our goal is to be able to relate molecular stracture, as depicted by stractural formulas and other types of stractural information, such as bond lengths and electronic distributions, to the chemical reactivity and physical properties of molecules. 

It is difficult to generalize regarding adhesion properties and physical characteristics of urethanes, because both the adhesion properties and physical properties can vary widely. One two-part urethane adhesive may be an outstanding adhesive for bonding SMC/SMC. Another urethane adhesive may fail miserably using the same SMC, due to delamination at the interface or adhesive failure. 

L. Manes (ed.) Structure and Bonding, Vol. 59/60, Actinides — Chemistry and Physical Properties, Springer, Berlin, 1985, 305 pp. 

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