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2.11.4.1.3 Method 3: Synthesis of Bis(η5-cyclopentadienyl)metal(IV) Complexes Containing Mono­halo and/or Group 16 or 15 Atom Ligands and Their Derivatives with Modified Cyclopentadienyl Ligands

DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032699.

Bis(η5-cyclopentadienyl)dihalozirconium(IV) and -hafnium(IV) complexes, and their analogues containing modified cyclopentadienyl groups, readily undergo displacement of the halogen atoms with various nucleophiles to produce compounds of the type [M(Cp)2XY] and [M(Cp)2Y2], and their derivatives, where X is a halogen and Y is a ligand containing a group 16 or 15 atom. In these ligand substitution reactions, both the substrates and the products are coordinatively unsaturated 16-electron species, which, in general, interact readily with a variety of nucleophiles or bases. From the perspective of organic synthesis, those products formed that contain two different σ-ligands are useful precursors to monoorgano-containing metallocene derivatives, as shown in the two-step conversion of dichlorobis(η5-cyclopentadienyl)zirconium(IV) (49) into chlorobis(η5-cyclopentadienyl)methylzirconium(IV) (51) via the oxo-bridged dizirconium complex 50 (Scheme 21).[‌63‌,‌64‌] This is similar for hafnium derivatives.[‌117‌,‌299‌]

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