INORGANIC and ORGANOMETALLIC COMPLEXES

The piezochromism of [Fe(CN)5(4CNpy)] and [Fe(CN)5(pz)] (and of the biferrocenium cation) was included in a wide-ranging solvatochromism/piezochromism correlation for metal-to-ligand (and ligand-to-metal) charge-transfer bands of a variety of inorganic and organometallic complexes. 

Charges Calculated on the Central Metal Atom in Inorganic and Organometallic Complexes Based on ab Initio Calculations... 

Inorganic and Organometallic Complexes Frequently used as Mediators in Aqueous Medium at 25 °C... 

This chapter concerns the study of electrode reaction mechanisms of inorganic and organometallic complexes. The emphasis is on proper use of experimental measurables from cyclic voltammetry for diagnosis of common mechanisms such as E, EC, CE, and ECE reactions. We employ the standard designation of electron transfer (et) reactions as E, and other chemical reactions as C. In practice, mechanistic studies make use of an array of electrochemical and other physical and chemical methods, but space limitations restrict our attention to the powerful and versatile technique of cyclic voltammetry (CV). If necessary, the reader may review the fundamentals of this technique in Chapter 3. 

Organoaluminum compounds also have applications in the synthesis of inorganic and organometallic complexes of the transition metals. Since aluminum is more electropositive than most of the transition metals, aluminum alkyls are excellent alkylating agents for transition metal complexes. Alkylation followed by subsequent -hydrogen and reductive elimination (e.g. equation 32) is a convenient means of reducing transition... 

Spectroscopic Characterization of Inorganic and Organometallic Complexes by Metal and High-Pressure NMR... 

Spectrophotometric Cell for Inorganic and Organometallic Complexes Under Inert Atmospheric Conditions... 

Roc (1987) CD spectroscopic characterization of inorganic and organometallic complexes by metal and high-pressure NMR. In Wayda AL and Darensbourg MV (eds.) Experimental Organometallic Chemistry, ACS Symposium Series No. 357, ch. 8. Washington, DC American Chemical Society. 

Another use of the d electron count is the determination of whether a metal has a nucleophilic orbital. Square planar complexes with d orbital counts above four have electrons in a dj2 orbital. This orbital is completely accessible because there are no ligands along the z axis. The orbital can act as a nucleophilic lone pair, much like a lone pair on a nitrogen atom. For example, in Rh(Cl)(CO)(PPh3)2, the metal is d and the complex is square planar. Hence, the structure is nucleophilic at Rh. However, the complex only has 16 electrons, and thus it is also electrophilic. This is not uncommon some inorganic and organometallic complexes can often accept and donate electrons, and the reactivity patterns reflect this. 

---