Mechanochemistry is a powerful tool for developing clean and energy-efficient chemical transformations in organic and inorganic chemistry, supramolecular chemistry, cocrystallization, as well as materials science.1 Despite the successes of mechanochemistry in the above mentioned fields, currently one area that remains largely undeveloped is organometallic chemistry.2 This presentation will highlight our recent work on a model organometallic system, demonstrating a new and clean mechanochemical methodology for the bromination of organometallic Re(I) complexes, such as CpRe(CO)3, and the control over isomeric composition of the product (Figure 1). The presentation will compare the traditional solution-based methodologies for the synthesis of cyclopentadienyl dibromodicarbonylrhenium complexes3 to our solvent-free or liquid-assisted grinding (LAG) mechanochemical approaches, and demonstrate the superior nature of mild mechanochemical synthesis in terms of time, yield, purity and control of product structure.Figure 1  . X-ray structure of trans-CpRe(CO)2Br2 obtained by mechanical milling. References 1. James, S. L.; Adams, C. J.; Bolm, C.; Braga, D.; Collier, P.; Fri�cic, T. et al. Chem. Soc. Rev. 2012 , 41, 413-447.2. Bala, M. D.; Coville, N. J. J. Organomet. Chem. 2007 , 692, 709-730.3. Nesmeyanov, A. N.; Kolobova, N. E.; Makarov, Yu. V.; Ahisimov, K. N.; Izv. Akad. Nauk SSSR, Ser. Khim. 1969 , 1826.

Development of mechanochemistry for organometallic synthesis

246th National Meeting (2013)

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