Introduction
The complex Cp2Zr(py)(Me3SiC≡CSiMe3) is a dark purple to black solid and was first synthesized by Uwe Rosenthal and co-workers in 1995.[1] The applications are to some extent similar to those of the Negishi reagent,[2] but Rosenthal’s zirconocene provides some considerable advantages:[3] it is stable in solutions of hydrocarbon solvents and as a solid, and it can be isolated and stored for several months in a glovebox without any noticeable decomposition. This lower reactivity of Rosenthal’s zirconocene in comparison with the Negishi reagent is accompanied by a higher selectivity, broadening the scope of its applications. It plays an important role in organic and inorganic synthesis, as it forms for example zirconacyclopentadienes that can be transformed into a variety of different heterocycles.[4]
Rosenthal’s zirconocene 2 can be prepared in a one-pot procedure, starting with Cp2ZrCl2.[3]
[5] The THF intermediate 1 is unstable and difficult to isolate.[1] Therefore, this complex is treated in situ with pyridine, giving high yields of 2 (up to 85%).
Scheme 1 Preparation of Rosenthal’s reagent.