Structure and Bonding

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes
Holloway LR and Li L
The preparation and characterization of a representative group of novel non-heme metal nitrosyl complexes that have been synthesized over the last decade are discussed here. Their structures are examined and classified based on metal type, the number of metal centers present, and the type of ligand that is coordinated with the metal. The ligands can be phosphorus, nitrogen, or sulfur based (with a few exceptions) and can vary depending on the presence of chelation, intermolecular forces, or the presence of other ligands. Structural and bonding characteristics are summarized and examples of reactivity regarding nitrosyl ligands are given. Some of the relevant physical chemical properties of these complexes, including IR, EPR, NMR, UV-vis, cyclic voltammetry, and X-ray crystallography are examined.
The Periodic Table's Impact on Bioinorganic Chemistry and Biology's Selective Use of Metal Ions
Bhagi-Damodaran A and Lu Y
Despite the availability of a vast variety of metal ions in the periodic table, biology uses only a selective few metal ions. Most of the redox active metals used belong to the first row of transition metals in the periodic table and include Fe, Co, Ni, Mn and Cu. On the other hand, Ca, Zn and Mg are the most commonly used redox inactive metals in biology. In this chapter, we discuss the periodic table's impact on bio-inorganic chemistry, by exploring reasons behind this selective choice of metals biology. A special focus is placed on the chemical and functional reasons why one metal ion is preferred over another one. We discuss the implications of metal choice in various biological processes including catalysis, electron transfer, redox sensing and signaling. We find that bioavailability of metal ions along with their redox potentials, coordination flexibility, valency and ligand affinity determine the specificity of metals for biological processes. Understanding the implications underlying the selective choice of metals of the periodic table in these biological processes can help design more efficient catalysts, more precise biosensors and more effective drugs.