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Solvent-Free Organometallic Reactivity: Synthesis of Hydride and Carboxylate Complexes of Uranium and Yttrium from Gas/Solid Reactions

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journal contribution
posted on 13.01.2014, 00:00 by Christopher L. Webster, Joseph W. Ziller, William J. Evans
Gas/solid reactions involving H2 and CO2 with the metallocenes (C5Me5)2UMe2 and (C5Me5)2U­(allyl)2 as solids in the absence of solvent provide an improved method to make organouranium hydride and carboxylate products. Decomposition products that can form in solution from the reactive hydrides can be avoided by this method, and this approach can also provide intermediates too reactive to isolate in some solution reactions. In contrast to the variable nature of the hydrogenolysis reaction of (C5Me5)2UMe2 in toluene that forms byproducts along with the mixture of [(C5Me5)2UH2]2 and [(C5Me5)2UH]2, a byproduct-free hydrogenolysis occurs when (C5Me5)2UMe2 in the solid state is treated with H2 gas to form predominantly [(C5Me5)2UH2]2. H2 reacts with solid (C5Me5)2U­(C3H5)2 and (C5Me5)2U­(C3H5) similarly. The reaction of CO2 (80 psi) with solid (C5Me5)2UMe2 forms the monocarboxylate (C5Me5)2U­(O2CCH32O,O′)­Me, in contrast to the solution reaction that forms the diacetate (C5Me5)2U­(O2CCH32O,O′)2 in minutes. The reaction of H2 with solid (C5Me5)2Y­(C3H5) provided (C5Me5)2Y­(μ-H)­YH­(C5Me5)2 without the decomposition products that it forms in solution such that single crystals suitable for X-ray diffraction could be isolated for the first time.