Zirconium & Hafnium: Organometallic ChemistryBased in part on the article Zirconium & Hafnium: Organometallic Chemistry by Bernard Gautheron, Roland Broussier, & Philippe Meunierk which appeared in the Encyclopedia of Inorganic Chemistry, First Edition .

Abstract

This review considers the main aspects of organometallic chemistry of zirconium and hafnium during the last 10 years. It is complementary to the first edition of Encyclopedia of Inorganic Chemistry. The material is presented in two major parts divided in five and three sections respectively. The first part is devoted to syntheses: the first section, by far the largest, covers in a systematic manner bis and mono cyclopentadienyl complexes with +4, +3, and +2 oxidation states and more especially constrained‐geometry (CG) complexes, cationic complexes, and anionic or zwitterionic 18‐electron complexes; unusual coordination geometries at carbon stabilized by group 4 metallocenes are presented in the second section; other anionic π‐ligands complexes and also lacking π‐ligands complexes are considered in two different sections and bimetallics are developed in the last section. Applications in metal‐mediated organic synthesis and catalysis are reviewed in the second part: neutral organozirconium complexes in organic and organometallic syntheses (hydrozirconation and carbozirconation), cationic zirconocenes in organic synthesis and catalysis, and organozirconium complexes in asymmetric catalysis.