Unusual Intramolecular Motion of ReH92– in K2ReH9 Crystal: Circle Dance and Three-Arm Turnstile Mechanisms Revealed by Computational Studies

The nonahydridorhenate dianion ReH92– is a unique rhenium polyhydride complex due to its remarkably high coordination number; however, its detailed polytopal rearrangement process in either solution or crystal is so far unclear. In this work, our quantum chemical calculations have identified two previously unreported fluxional mechanisms for the ReH92– dianion in the K2ReH9 crystal: three-arm turnstile rotation and circle dance mechanism. These two polytopal rearrangements in the crystal offer an alternative interpretation to the pulse and wide-line NMR spectra (Farrar et al. J. Chem. Phys. 1969, 51, 3595). The previously postulated hindered rotation of the whole ReH92– dianion in K2ReH9 (White et al. J. Chem. Soc., Faraday Trans. 2 1972, 68, 1414) turns out to be a combination of the above-mentioned two elementary fluxional processes. In addition, our calculations have confirmed the Muetterties’ D3h⇌C4v rearrangement as the intramolecular motion for the ReH92– dianion in solution.