The Preparation of Tetramethyl 1,1′,3,3′-Ruthenocenetetra­carboxylate and Tetramethyl 1,1′,3,3′-Osmocenetetracarboxylate, and a Simplified Synthesis for Tetramethyl 1,1′,3,3′-Ferrocene­tetracarboxylate

Dedicated to Jean-Pierre Praly on his 70^th birthday

Abstract

Substituted metallocenes with more than two substituents have to be synthesized using doubly substituted cyclopentadiene rings in a reaction with a metal compound or by the introduction of additional functional groups to an already di-substituted metallocene. The direct formation of tetra-substituted metallocenes often suffers due to insufficient reactivity of the reagents or the resulting product mixtures, which are hard to separate. In this work, a protocol, which was successful in a tetra-substitution of ferrocene by a tetra-metalation followed by a reaction with carbon dioxide, is used to perform the tetra-substitution of ruthenocene and osmocene. In addition, a simplified protocol for the tetra-functionalization of ferrocene using commercially available components on a medium scale is described.

Key words

metallocene - deprotometalation - ruthenocene - osmocene - alkali metal - superbase

• References

• 1 Heinze K, Lang H. Organometallics 2013; 32: 5623
• 2 Astruc D. Eur. J. Inorg. Chem. 2017; 6
• 3 Petrov AR, Jess K, Freytag M, Jones PG, Tamm M. Organometallics 2013; 32: 5946
• 4 Förster C, Heinze K. Z. Anorg. Allg. Chem. 2015; 641: 517
• 5 Roemer M, Nijhuis CA. Dalton Trans. 2014; 43: 11815
• 6 Sanders R, Mueller-Westerhoff UT. J. Organomet. Chem. 1996; 512: 219
• 7a Halasa AF, Tate DP. J. Organomet. Chem. 1970; 24: 769
• 7b Benkeser RA, Nagai Y, Hooz J. J. Am. Chem. Soc. 1964; 86: 3742
• 8 Clegg W, Henderson KW, Kennedy AR, Mulvey RE, O’Hara CT, Rowlings RB, Tooke DM. Angew. Chem. Int. Ed. 2001; 40: 3902
• 9 Clegg W, Crosbie E, Dale-Black SH, Hevia E, Honeyman GW, Kennedy AR, Mulvey RE, Ramsay DL, Robertson SD. Organometallics 2015; 34: 2580
• 10 Hildebrandt A, Al Khalyfeh K, Schaarschmidt D, Korb M. J. Organomet. Chem. 2016; 804: 87
• 11a Schlosser M. Pure Appl. Chem. 1988; 60: 1627
• 11b Lochmann L, Janata M. Cent. Eur. J. Chem. 2014; 12: 537
• 12 Bauer W, Lochmann L. J. Am. Chem. Soc. 1992; 114: 7482
• 13 Schrock RR, Fellmann JD. J. Am. Chem. Soc. 1978; 100: 3359
• 14 Fraenkel G, Chow A, Winchester WR. J. Am. Chem. Soc. 1990; 112: 6190
• 15 Benrath P, Kaiser M, Limbach T, Mondeshki M, Klett J. Angew. Chem. Int. Ed. 2016; 55: 10886
• 16 Kaiser M, Klett J. Dalton Trans. 2018; 47: 12582
• 17 Screttas CG, Steele BR. J. Organomet. Chem. 1993; 453: 163
• 18 Jennewein B, Kimpel S, Thalheim D, Klett J. Chem. Eur. J. 2018; 24: 7605
• 19 Deschenaux R, Kosztics I, Nicolet B. J. Mater. Chem. 1995; 5: 2291
• 20 Micallef LS, Loughrey BT, Healy PC, Parsons PG, Williams ML. Organometallics 2011; 30: 1395
• 21 Langheim D, Wenzel M, Nipper E. Chem. Ber. 1975; 108: 146
• 22 Andrikopoulos PC, Armstrong DR, Clegg W, Gilfillan CJ, Hevia E, Kennedy AR, Mulvey RE, O’Hara CT, Parkinson JA, Tooke DM. J. Am. Chem. Soc. 2004; 126: 11612
• 23 Inorganic Reactions and Methods, Volume 11, The Formation of Bonds to C, Si, Ge, Sn, Pb (Part 3). Zuckerman JJ, Hagen AP. Wiley; New York: 2009
• 24 Waniek SD, Klett J, Förster C, Heinze K. Beilstein J. Org. Chem. 2018; 14: 1004
• 25 Wiebe A, Gieshoff T, Möhle S, Rodrigo E, Zirbes M, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 5594
• 26 Presser A, Hüfner A. Monatsh. Chem. 2004; 135: 1015