ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The mechanism of ligand substitution in 17- and 19-electron organometallic radicals is discussed. These species substitute ligands by an associative process some 106 to 1010 faster than analogous 18-electron complexes. When 17-electron species can be generated by bond homolysis or electron transfer reactions of 18-electron complexes, they can act as intermediates in radical chain reactions of 18-electron complexes. A 17-19 electron rule is proposed to explain transformations of organometallic radicals just as the 16-18 electron rule finds use for closed shell organometallic complexes. The origin of this rule is the favorable two-center three-electron bond that can form when an odd electron in a sterically accessible metal d-orbital interacts with an electron pair on an entering nucleophile. Besides simple substitution, these radicals can disproportionate, dimerize, and undergo insertion or atom abstraction reactions.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550191107
