Rosenthal’s Zirconocene

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]

• References

• 1 Rosenthal U, Ohff A, Baumann W, Tillack A, Görls H, Burlakov VV, Shur VB. Z. Anorg. Allg. Chem. 1995; 621: 77
• 2 Negishi E, Holmes SJ, Tour JM, Miller JA, Cederbaum FE, Swanson DR, Takahashi T. J. Am. Chem. Soc. 1989; 111: 3336
• 3 Linshoeft J, Baum EJ, Hussain A, Gates PJ, Näther C, Staubitz A. Angew. Chem. Int. Ed. 2014; DOI: 10 1002/anie.201407377.
• 4a Fagan PJ, Nugent WA. J. Am. Chem. Soc. 1988; 110: 2310
• 4b Fagan PJ, Nugent WA, Calabrese JC. J. Am. Chem. Soc. 1994; 116: 1880
• 5 Nitschke JR, Zürcher S, Tilley TD. J. Am. Chem. Soc. 2000; 122: 10345
• 6 Lucht BL, Buretea MA, Tilley TD. Organometallics 2000; 19: 3469
• 7 Miller AD, Tannaci JF, Johnson SA, Lee H, McBee JL, Tilley TD. J. Am. Chem. Soc. 2009; 131: 4917
• 8 Parker D. Macrocycle Synthesis: A Practical Approach. Oxford University Press; Oxford: 1996
• 9 Tannaci JF, Kratter IH, Rider EA, McBee JL, Miller AD, Tilley TD. Chem. Commun. 2009; 233
• 10 Haehnel M, Hansen S, Schubert K, Arndt P, Spannenberg A, Jiao H, Rosenthal U. J. Am. Chem. Soc. 2013; 135: 17556
• 11 Kaleta K, Arndt P, Beweries T, Spannenberg A, Theilmann O, Rosenthal U. Organometallics 2010; 29: 2604
• 12 Kaleta K, Ruhmann M, Theilmann O, Roy S, Beweries T, Arndt P, Villinger A, Jemmis ED, Schulz A, Rosenthal U. Eur. J. Inorg. Chem. 2012; 611
• 13 Kaleta K, Ruhmann M, Theilmann O, Beweries T, Roy S, Arndt P, Villinger A, Jemmis ED, Schulz A, Rosenthal U. J. Am. Chem. Soc. 2011; 133: 5463