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2.11.10.1 Method 1: Synthesis of Bis(η5-cyclopentadienyl)metal(IV) “Ate” Complexes

DOI: 10.1055/sos-SD-002-00797

Negishi, E.-i.; Takahashi, T.Science of Synthesis, (20032813.

The reactions of the 16-electron complexes [Zr(Cp)2Cl2], [Zr(Cp)2R1X], and [Zr(Cp)2R1R2], and related derivatives with organometals containing alkali metals, in particular lithium, or magnesium can, in principle, lead to the formation of compounds of the type M[Zr(Cp)2R1R2R3] and related derivatives, where M is lithium, magnesium halide, etc., and Rn is a carbon group. In reality, however, these reactions can be much more complicated than depicted above. Those reactions in which all carbon groups are simple alkyl and/or aryl groups are discussed in Section 2.11.10.1.1. Those reactions that involve one or more alkynyl groups not only lead to the formation of alkynylzirconates, but also induce a novel migratory insertion reaction (Section 2.11.10.2.1). In fact, the use of α-hetero-substituted alkyl- and alkenyllithiums can undergo more readily predictable migratory insertion reactions that are similar to those that have been observed with boron reagents.[‌399‌] These reactions are discussed in Section 2.11.10.2.2. As interesting and potentially useful as these above reactions are, the structures of the zirconate derivatives have rarely been identified by X-ray crystallography. However, some zwitterionic bis(η5-cyclopentadienyl)zirconium(IV) derivatives are stable and crystalline, permitting their identification by X-ray analysis (Section 2.11.10.2.3).

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