The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

/pdf/secondary-building-units-nets-and-bonding-in-the-chemistry-o0m4ttzsgz.pdf

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

The chemistry of N-heterocyclic carbenes has long been limited to metal coordination compounds derived from azolium precursors, a development that was started by Ofele and Wanzlick in 1968. Since free carbenes are now available through the work of Arduengo (1991), a renaissance in this little-recognized area of chemistry has occurred. A leading motive is the advantages of N-heterocyclic carbenes as ligands in organometallic catalysts, where they extend the scope of application reached by phosphanes (functionalized, chiral, water-soluble, and immobilized derivatives). The present review summarizes the state of the art with regard to synthesis, structure, bonding theory, metal coordination chemistry, and catalysis. Chelating, functionalized, chiral, and immobilized ligands can be generated and attached to metal centers in straightforward procedures under mild conditions. A wealth of new chemistry is thus opened. It is also shown how carbenes derived from imidazoles and triazoles behave as ligands in catalysis. It is reasonable to assume that N-heterocyclic carbenes surpass the ubiquitous phosphanes as ligands in a number of organometallic catalytic reactions.

N-Heterocyclic Carbenes†‡

Chemistry of biologically important synthetic organoselenium compounds.

Halogen bonding is the noncovalent interaction where halogen atoms function as electrophilic species. The energetic and geometrical features of the interaction are described along with the atomic characteristics that confer molecules with the specific ability to interact through this interaction. Halogen bonding has an impact on all research fields where the control of intermolecular recognition and self-assembly processes plays a key role. Some principles are presented for crystal engineering based on halogen-bonding interactions. The potential of the interaction is also shown by applications in liquid crystals, magnetic and conducting materials, and biological systems.

Halogen Bonding in Supramolecular Chemistry

Siliciumverbindungen mit starken intramolekularen sterischen wechselwirkungen: XIX. Simultane bildung und reaktionen von di-t-butylsilandiyl und tetra-t-butyldisilen

Bis(2,4,6-triisopropylphenyl)stannylene, formed by thermolysis of the cyclotristannane 4, reacts with 4,5-dimethyl-1,3-diisopropylimidazol-2-ylidene to furnish the adduct 8; an X-ray structural analysis of this compound reveals the presence of a long tin–carbon ‘double bond’ with a length of 237. 9(5) pm and a distinctly pyramidal tin centre.

A carbene–stannylene adduct with a long tin–carbon double bond?

The Reagent Diphenyldiselane/Iodine: No Phenylselenenyl Iodide but a Charge Transfer Complex with Cyclic Moieties

Directed Synthesis of [Mo3S13]2−, an Isolated Cluster Containing Sulfur Atoms in Three Different States of Bonding

Phosphasilirenes, Three‐Membered Rings Containing PC Double Bonds

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