Open shell organometallics: a general analysis of their electronic structure and reactivity

Transition metal organometallic compounds that contain fewer than 18-electrons and two or more unpaired electrons are generally excluded from treatises of either Werner-type coordination compounds or organometallic chemistry. However, they can be seen as the bridge filling the gap between these two traditional areas of coordination chemistry. Their magnetic and optical properties are reminiscent of the Werner-type complexes, whereas their chemical reactivity parallels that of the lower-valent organometallies. Spin state change phenomena are of paramount importance in this area. This paper provides a broad perspective of this area, with particular attention to: (i) how the ground state properties can be related to the metal and ligands nature; (ii) under which circumstances the often inappropriately invoked concept of spin block is meaningful; (iii) the spin acceleration concept; (iv) how the coordination sphere affects the topology of the reaction coordinate in the vicinity of spin crossing points; and (v) the effect of spin state changes on reaction selectivities. (C) 2004 Elsevier B.V. All rights reserved.