Electronic Configuration, Oxidation States, Structures

The application of MOssbauer spectroscopy to silicate mineralogy has been well described in two papers by Bancroft et al, in which the influences of electronic configuration, oxidation state, and coordination symmetry of the iron cations were correlated firstly with silicates of known structures [212], and latterly with silicates of unknown and complex structures [213]. Most of the data discussed here are taken from these works, but references are given where appropriate to other data available. Silicate minerals of lunar origin are discussed on p. 294. 

This chapter is intended to provide a unified view of selected aspects of the physical, chemical, and biological properties of the actinide elements. The f block elements have many unique features, and a comparison of the lanthanide and actinide transition series provides valuable insights into the properties of both. Comparative data are presented on the electronic configurations, oxidation states, redox potentials, thermochemical data, crystal structures, and ionic radii of the actinide elements, together with a miscellany of topics related to their environmental and health aspects. Much of this material is assembled in tabular and graphical form to facilitate rapid access. Many of the topics covered in this chapter, and some that are not discussed here, are the subjects of subsequent chapters of this work, and these may be consulted for more comprehensive treatments. This chapter provides a welcome opportunity to discuss the biological and environmental aspects of the actinide elements, subjects that were barely mentioned in the first edition of this work but have assumed great importance in recent times. 

In contrast to chloride compounds, niobium oxides have a VEC of 14 electrons, due to an overall anti-bonding character of the a2u state, caused by a stronger Nb-O anti-bonding contribution. In some cases, the VEC cannot be determined unambiguously due to the uncertainty in the electron distribution between the clusters and additional niobium atoms present in the majority of the structures. The 14-electron compounds exhibit semiconducting properties and weak temperature-independent paramagnetism. Unlike niobium chlorides, the oxides do not exhibit a correlation between the electronic configuration and intra-cluster bond distances. 

In the unstable +2 oxidation state, the valence electron configuration of the group 14 elements corresponds to a completely filled ns orbital. However, the lone pair located at the central metal has often steric influence on the structure. 

Specific examples are now used to demonstrate these concepts. First, consider the group Ru(bpy)j2+ (luminescent), Os(bpy)32+ (slightly luminescent), and Fe(bpy)32+ (nonluminescent) (Table4.1). For Fe(bpy)32+, despite an exhaustive search no emission has ever been detected even at 77K we routinely use it as a nonemissive solution filter. All three iso structural eft systems are in the same oxidation state with the same electronic configuration (ft6). The Fe(II) complex has an intense MLCT band at 510 nm, and the Ru(II) complex at 450 nm the Os(II) complex has intense MLCT bands that stretch out to 700 nm. The n-n transitions are all quite similar in all three complexes with intense absorptions around 290 nm and ligand triplet states at 450 nm (inferred from the free ligand and other emissive complexes and the insensitivity of these states to coordination to different metals). 

The oxidation state of Ge atoms and linking metal atoms in the framework structure was probed by X-ray photoelectron spectroscopy (Fig. 15). The XPS spectra suggest that the Ge and linking metal atoms are in relatively low oxidation state and have electronic configuration similar to those observed in metal-alloy phases [57]. 

Platinum(IV) has six valency electrons, and a regular octahedral configuration is to be expected in its compounds, as is indeed found to be the case 257). The need for six ligands while the oxidation state is only four leads to some very unusual structures. 

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