Solid-state compounds metal properties

The structural relationship between the molecular and solid-state compounds has been a hot issue in inorganic chemistry for some time (25-27). The extrusion (or excision) from preformed solid-state cluster compounds is one of the major synthetic methods of the preparation of cluster complexes (26). Use of cluster complexes as precursors to solid-state cluster compounds is the reverse reaction of excision. Both reactions utilize the structural similarity of the metal cluster units. The basic cluster units of polyhedra (deltahedra) or raft structures are triangles, and both molecular and solid-state clusters with octahedral, tetrahedral, and rhomboidal cores have been reported. Similarity of other properties such as electronic structures based on the cluster units is also important. The present review is concerned with the syntheses and structures of the cluster complexes of the group 6 metals and with their relationships to solid-state chemistry. 

A pseudo salt is a compound that has some of the normal characteristics of a salt, but lacks certain others, notably the ionic lattice in the solid state and the property of ionizing completely in solution. The absence of these properties is due to the fact that the bonds between the metallic and nonmetallic radicals are covalent or semicovalent instead of polar. Because these salts do not ionize completely, they are also called weak salts. 

Solid state compounds of uranium have been much studied because of their unusual magnetic properties and their inertness. They are usually made by direct interaction with uranium metal. 

The simplicity of the tropolone molecule belies its fascinating character in both solution and the solid state. The aromatic properties of these compounds make varied interactions observable in the solid state including hydrogen tunnelling, tt-tt stacking and bromo... bromo interactions. The addition of a metal centre does not suppress this character, but can instead add further dimensions to the complexes formed. Palladium(II) complexes with tropolone can result in a myriad products, in which tropolone can act as a source of bromo moieties to assist in the reaction path. Although only a small fraction of our research team s work has been presented, the... 

The topics chosen for inclusion in this chapter reflect areas of active interest and elaborate upon some topics that have been given only brief mention in earlier chapters. In describing the chemistries of the d- and /-block metals in Chapters 21,22 and 24, we included many examples of solid state compounds, and we now look further at electrical conducting and superconducting properties. At various points in the book, we have mentioned colour pigments in ceramic materials when... 

Nitrogenase is another big target of cluster synthesis. The X-ray elucidation of the active center of the Fe-Mo cofactor and P-cluster (5) has accelerated the efforts to find rational preparative methods of trinuclear or cubane-type clusters containing molybdenum (6-9). The raft cores in these cluster complexes are one of the general structural units also in solid-state compounds, and the mutual relationships are very important. A number of review articles are now available on the syntheses, structures, and other properties of metal chalcogenide cluster compounds (6, 7,10-24). 

Binary compounds can be made with uranium. Such solids state compounds have been investigated because they have interesting magnetic properties. They are made by direct interaction with uranium metal. Oxides mainly form with the general formula UO2, UjOg, UO2. The metal also reacts with other elements such as boron, carbon, nitrogen, phosphorus, and arsenic to make semi-metallic solids. Compounds can also be made using silicon, sulfur, selenium, and tellurium. Urinates can be formed by the addition of uranium with alkali and alkaline Earth metals. 

Exothermic Decompositions These decompositions are nearly always irreversible. Sohds with such behavior include oxygen-containing salts and such nitrogen compounds as azides and metal styphnates. When several gaseous products are formed, reversal would require an unlikely complex of reactions. Commercial interest in such materials is more in their storage properties than as a source of desirable products, although ammonium nitrate is an important explosive. A few typical exampes will be cited to indicate the ranges of reaction conditions. They are taken from the review by Brown et al. ( Reactions in the Solid State, in Bamford and Tipper, Comprehensive Chemical Kinetics, vol. 22, Elsevier, 1980). 

This section considers a number of extremely important structure types in which A1 combines with one or more other metals to form a mixed oxide phase. The most significant of these from both a theoretical and an industrial viewpoint are spinel (MgAl204) and related compounds, Na- -alumina (NaAlnOi ) and related phases, and tricalcium aluminate (Ca3Al20g) which is a major constituent of Portland cement. Each of these compounds raises points of fundamental importance in solid-state chemistry and each possesses properties of crucial significance to... 

Solid solutions are very common among structurally related compounds. Just as metallic elements of similar structure and atomic properties form alloys, certain chemical compounds can be combined to produce derivative solid solutions, which may permit realization of properties not found in either of the precursors. The combinations of binary compounds with common anion or common cation element, such as the isovalent alloys of IV-VI, III-V, II-VI, or I-VII members, are of considerable scientific and technological interest as their solid-state properties (e.g., electric and optical such as type of conductivity, current carrier density, band gap) modulate regularly over a wide range through variations in composition. A general descriptive scheme for such alloys is as follows [41]. 

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