Dynamic stereochemical rearrangements in chiral organometallic complexes

• Published in: Chemical Society reviews 2007-03, Vol.36 (3), p.551-569
• Main Author: Heard, Peter J
• Format: Article
• Language: English
• Subjects: Ligands; Molecular Structure; Organometallic Compounds - chemistry; Stereoisomerism
• ISSN: 0306-0012; 1460-4744
• DOI: 10.1039/b514855n

Organometallic complexes have long been known to display a wide variety of dynamic stereochemical processes. Classic examples of such processes include the exchange of axial and equatorial environments in trigonal bipyramidal complexes, such as Fe(CO)(5), and the migration of the metal moiety round the periphery of the cyclopentadiene ring in eta(1)-bound Cp complexes. The systematic study of fluxional processes is of interest because it can not only help provide a detailed, quantitative 'picture' of the bonding between the metals and ligands involved, but it can also help to rationalise chemical reactivity patterns. The introduction of chirality into organometallic complexes, usually in the form of a non-racemic chiral ligand, has led to an explosion in the importance such species, particularly with regard to their applications in organic functional group transformations. The presence of a chiral centre can also provide an excellent spectroscopic handle on the complex in question, enabling both novel fluxional processes to be observed and new light to be shed on old (unresolved) problems. In this critical review (101 references) the literature on metal-centred fluxional rearrangements in chiral transition and main group organometallic complexes is reviewed, complementing the recent review by Faller (see reference 8).