Abstract
Rhodium is used for a number of large processes that rely on homogeneous rhodiumβcatalyzed reactions, for instance rhodiumβcatalyzed hydroformylation of alkenes, carbonylation of methanol to acetic acid and hydrodesulfurization of thiophene derivatives (in crude oil). Many laboratory applications in organometallic chemistry and catalysis involve organorhodium chemistry and a wealth of rhodium coordination compounds is known. For these and other areas, ^103^Rh NMR spectroscopy appears to be a very useful analytical tool. In this review, most of the literature concerning ^103^Rh NMR spectroscopy published from 1989 up to and including 2003 has been covered. After an introduction to several experimental methods for the detection of the insensitive ^103^Rh nucleus, a discussion of factors affecting the transition metal chemical shift is given. Computational aspects and calculations of chemical shifts are also briefly addressed. Next, the application of ^103^Rh NMR in coordination and organometallic chemistry is elaborated in more detail by highlighting recent developments in measurement and interpretation of ^103^Rh NMR data, in relation to rhodiumβassisted reactions and homogeneous catalysis. The dependence of the ^103^Rh chemical shift on the ligands at rhodium in the first coordination sphere, on the complex geometry, oxidation state, temperature, solvent and concentration is treated. Several classes of compounds and special cases such as chiral rhodium compounds are reviewed. Finally, a section on scalar coupling to rhodium is provided. Copyright Β© 2004 John Wiley & Sons, Ltd.