Modulation of the Bonding between Copper and a Redox-Active Ligand by Hydrogen Bonds and Its Effect on Electronic Coupling and Spin States.

The exchange coupling of electron spins can strongly influence the properties of chemical species. The regulation of this type of electronic coupling has been explored within complexes that have multiple metal ions but to a lesser extent in complexes that pair a redox-active ligand with a single metal ion. To bridge this gap, we investigated the interplay among the structural and magnetic properties of mononuclear Cu complexes and exchange coupling between a Cu center and a redox-active ligand over three oxidation states. The computational analysis of the structural properties established a relationship between the complexes' magnetic properties and a bonding interaction involving a dx2-y2 orbital of the Cu ion and π orbital of the redox-active ligand that are close in energy. The additional bonding interaction affects the geometry around the Cu center and was found to be influenced by intramolecular H-bonds introduced by the external ligands. The ability to synthetically tune the d-π interactions using H-bonds illustrates a new type of control over the structural and magnetic properties of metal complexes.

C-H Bond Cleavage by Bioinspired Nonheme Metal Complexes.

The functionalization of C-H bonds is one of the most challenging transformations in synthetic chemistry. In biology, these processes are well-known and are achieved with a variety of metalloenzymes, many of which contain a single metal center within their active sites. The most well studied are those with Fe centers, and the emerging experimental data show that high-valent iron oxido species are the intermediates responsible for cleaving the C-H bond. This Forum Article describes the state of this field with an emphasis on nonheme Fe enzymes and current experimental results that provide insights into the properties that make these species capable of C-H bond cleavage. These parameters are also briefly considered in regard to manganese oxido complexes and Cu-containing metalloenzymes. Synthetic iron oxido complexes are discussed to highlight their utility as spectroscopic and mechanistic probes and reagents for C-H bond functionalization. Avenues for future research are also examined.

Stabilizing a NiII-aqua complex via intramolecular hydrogen bonds: synthesis, structure, and redox properties.

Hydrogen bonds within the secondary coordination sphere are effective in controlling the chemistry of synthetic metal complexes. Coupling the capacity of hydrogen bonds with those of redox-active ligands offers a promising approach to enhance the functional properties of transition metal complexes. These qualities were successfully illustrated with the [NNN]3-pincer ligand N,N' -(azanediylbis(2,l-phenylene))bis(2,4,6-triisopropyl-benzene-sulfonamido ([ibaps]3-) through the preparation of the NiII-OH2 complex, [NiII(ibaps)(OH2)]-. The [ibaps]3- ligand contains two appended sulfonamido groups that support the formation of intramolecular hydrogen bonds. The bulky 2,4,6-triisopropylphenyl rings are necessary to ensure that only one ligand binds to a single metal ion. The molecular structure of the complex shows a square planar N3O primary coordination sphere and two intramolecular hydrogen bonds involving the aqua ligand. Electrochemical measurements in acetonitrile revealed two oxidation events at potentials below that of the ferrocenium/ferrocene couple. Oxidation with 1 equiv of ferrocenium produced the one-electron oxidized species, [Ni(ibaps)(OH2)]. Experimental and computational studies support this assignment.