Advances in Inorganic Chemistry 

About: Advances in Inorganic Chemistry is an academic journal published by Elsevier BV. The journal publishes majorly in the area(s): Catalysis & Ligand. It has an ISSN identifier of 0898-8838. Over the lifetime, 341 publications have been published receiving 20773 citations. The journal is also known as: Inorganic chemistry.

Reduction potentials involving inorganic free radicals in aqueous solution

Abstract: Publisher Summary This chapter discusses the reduction potentials involving inorganic free radicals in aqueous solution. Because free radicals are usually transients, knowing their thermodynamic properties is primarily useful in mechanistic studies. Thus, the useful redox couples associated with a given free radical correspond to plausible elementary steps in reaction mechanisms. All potentials are expressed against the normal hydrogen electrode (NHE). Apart from the NHE, the standard state for all solutes is the unit molar solution at 25 °C. This violates the usual convention for species, such as O 2 that occur as gases, but because the rates of bimolecular reactions in solution are significant, the unit molar standard state is most convenient. The emphasis is on electron transfer reactions in which no bonds are formed or broken, electron transfer reactions in which concerted electron transfer and bond cleavage could occur, and certain atom transfer reactions. The chapter also presents a tabulation of ∆ f G ° values for all the radicals. A common approach in estimating the thermochemistry of aqueous free radicals is to use gas-phase data with approximations of solvation energies.

Density-Functional Theory of Spin Polarization and Spin Coupling in Iron—Sulfur Clusters

Abstract: Publisher Summary This chapter discusses recent progress toward the development of a unified picture of the electronic structures and spin interactions of iron–sulfur and related systems; these concepts provide a close connection between a spin Hamiltonian description and a more detailed orbital picture of the electron distribution. The iron–sulfur proteins and synthetic analogs are challenging systems for quantum mechanical methods because they contain a large number of electrons and because spin polarization and spin coupling are essential features of the complexes. Standard approaches of ab initio quantum chemistry start from a spin-restricted picture, which is poorly adapted to problems involving high-spin transition metal centers. For this reason, a combination has been developed of broken symmetry and spin-unrestricted methods that is particularly well adapted to study spin-polarized and spin-coupled systems. These ideas are well adapted for use with density-functional methods. In the chapter, the basic ideas are developed of this approach, using a perturbation theory formalism to rationalize the spin Hamiltonian and energy-splitting formulas that should be appropriate for spin-coupled transition metal clusters.

Structures of Organonitrogen—Lithium Compounds: Recent Patterns and Perspectives in Organolithium Chemistry

Abstract: Publisher Summary This chapter discusses the current patterns and perspectives in organolithium chemistry, including the structures of organonitrogenlithium (N-Li) compounds. The chapter explains the compounds with N-Li bonds. These are chiefly lithium imides [iminolithiums (RR’C=NLi) n ] and their complexes with added Lewis bases (L), and lithium amides [amidolithiums (RR’NLi) n ] and their complexes. For the lithium amide species, particularly, only those whose R,R’ groups that do not contain additional functionalities are described—that is, the R,R’ groups remain largely uninvolved with lithium centers. These species are termed “simple” lithium amides. N-Li compounds and, particularly, lithium amides (R 2 NLi) are widely used both in organic and in organometallic syntheses. For the former, these strong bases are employed as proton abstractors to generate new organolithiums. Although synthetic uses have dominated the interest in N-Li compounds, the chapter focuses on the structures. Most of the physical properties of organolithium compounds (the marked exception being conductance) arise, because of the overall size and shape of the units making up these materials and the nature of the peripheries of these units. The basic structural building block of any organolithium is an ion pair, R – L + . The identities and structures of complexed organolithiums are of particular importance.

Toward the Construction of Functional Solid-State Supramolecular Metal Complexes Containing Copper(I) And Silver(I)

Abstract: Publisher Summary This chapter discusses construction of functional solid-state supramolecular metal complexes containing copper (I) and silver (I). The copper(I) and silver(I) ions are regarded as extremely soft acids favoring coordination to soft bases, such as ligands containing S and unsaturated N. Copper(I) and silver(I) complexes with these soft ligands give rise to an interesting array of stereochemistries and geometric configurations, with the coordination numbers of two to six all occurring. The most common stereochemistries for both ions are the linear two-coordinate and the tetrahedral four-coordinate geometries with some distortions of the environment, particularly in the presence of chelating type ligands, attributable to the spherical dl0 configuration. On the basis of resonance Raman spectra, the lowest excited state in the polymer is assigned to the Cu(I)-topyrazine metal-to-ligand charge-transfer excited state. Successful construction of multidimensional frameworks largely relies on ligand design to suit different geometries and coordination numbers of the metal ions.

Intervalence Charge Transfer and Electron Exchange Studies of Dinuclear Ruthenium Complexes

Abstract: Publisher Summary This chapter discusses the theory of mixed-valence systems and theory of electron exchange. In the case of strong coupling, for which it is no longer appropriate to use perturbation theory, the interaction of states is so great that bonding and antibonding potential energy curves result. Because the ground state is delocalized between metal ions, it is not strictly appropriate to describe the intervalence transition band of a class III complex as a metal-to-metal charge transfer transition. The metal-to-metal charge transfer (MMCT) designation is used for the sake of simplicity. The dependence of intervalence transition energy on the activation barrier to thermal electron transfer allows the solvent dependence of intervalence transitions to be understood in terms of relationships developed for the Marcus Theory of electron transfer. The Hush model is the preferred method of analysis of mixed valence complexes for the experimentalist because of its readily understandable derivation, its overlap with the Marcus theory of electron transfer, and the facility of its application. However, it is applicable only to weakly coupled class II complexes. A quantitative theory that is applicable to all mixed valence complexes is desirable.