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Synthetic Utility of Tetrabutylammonium Salts in Uranium Metallocene Chemistry

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posted on 2016-02-09, 00:00 authored by Christopher L. Webster, Ryan R. Langeslay, Joseph W. Ziller, William J. Evans
Tetrabutylammonium chloride and nitrate salts react with (C5Me5)2UCl2 to expand the coordination sphere of the metallocene to form the formal 9- and 10-coordinate complexes, [NBu4]­[(C5Me5)2UCl2(NO3)], 1, and [NBu4]­[(C5Me5)2UCl2(NO3)], 2, respectively. Complex 2 displays modified reactivity compared to that of (C5Me5)2UCl2 in substitution reactions with Khpp [hpp =1,3,4,6,7,8-hexahydro-2H-pyrimido­(1,2-a)­pyrimidine] and K­(NC4Me4) in the synthesis of (C5Me5)2U­(hpp)­Cl, (C5Me5)­U­(hpp)3, and (C5Me5)2U­(NC4Me4)­Cl. The U3+ complex, [NBu4]­[(C5Me5)2UCl2], can be formed by reduction of 2 with K­(Hg), as well as with KC5Me5, K2C8H8, and Li3N.