Extensive rearrangement of complex fragments during solid/gas single-crystal to single-crystal transformations Joe Goodall, Andrew Weller, E.A. Thompson, L. R. Doyle, M.R. Gyton, H.T. Jenkins, J.M. Lynam University of York, UK The use of organometallic solid-state single-crystal to single-crystal (SC-SC) transformations is an emerging area of synthesis, reactivity and catalysis. 1, 2 A recurring problem with SC-SC transformations is that preservation of crystallinity throughout the transformation is often challenging due to the stress associated with the reaction. 1, 3 Here, the solid-state rearrangements during solid/gas reactions of manganese(I) and rhenium(I) pincer complexes with CO is shown to be highly dependent on the non-covalent interactions between the incoming ligand and the weakly coordinating anion. The reactions cause the crystals to undergo extensive cracking to form micron-sized crystals, which necessitated the use of microcrystal Electron Diffraction (microED) 4 for structural elucidation in the case of the manganese example. This report highlights the extreme plasticity of the solid-state, facilitated by the [BAr F 4 ] - anions and associated non-covalent interactions, as well as the capability of microED to facilitate structure determination of the products of solid/gas SC-SC reactions where macroscopic crystalline integrity is lost.
Figure 1: Solid-state rearrangement of [Mn( i Pr-PONOP)(THF)(CO) 2 ][BAr F
4 ] upon addition of CO in a single-crystal to single-
crystal transformation. References 1. K. A. Reid and D. C. Powers, Chem. Commun. , 2021, 57 , 4993-5003. 2. A. J. Martínez-Martínez, C. G. Royle, S. K. Furfari, K. Suriye and A. S. Weller, ACS Catal. , 2020, 10 , 1984-1992. 3. A. J. Bukvic, A. L. Burnage, G. J. Tizzard, A. J. Martínez-Martínez, A. I. McKay, N. H. Rees, B. E. Tegner, T. Krämer, H. Fish, M. R. Warren, S. J. Coles, S. A. Macgregor and A. S. Weller, J. Am. Chem. Soc. , 2021, 143 , 5106-5120. 4. C. G. Jones, M. W. Martynowycz, J. Hattne, T. J. Fulton, B. M. Stoltz, J. A. Rodriguez, H. M. Nelson and T. Gonen, ACS Cent. Sci. , 2018, 4 , 1587-1592.
P06
© The Author(s), 2023
Made with FlippingBook Learn more on our blog