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Reaction Chemistry of the U3+ Metallocene Amidinate (C5Me5)2[iPrNC(Me)NiPr]U Including the Isolation of a Uranium Complex of a Monodentate Acetate

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posted on 15.02.2010, 00:00 authored by William J. Evans, Justin R. Walensky, Joseph W. Ziller
The reductive chemistry of U3+ in the metallocene amidinate coordination environment of (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U, 1, has been explored. Two equivalents of 1 react with PhSSPh and 2,2-dithiopyridine (pySSpy) to produce (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(SPh), 2, and (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]U(Spy), 3, respectively. Complexes 2 and 3 can also be synthesized through insertion of iPrNCNiPr into the methyl group in (C5Me5)2UMe(SPh) and (C5Me5)2UMe(Spy), 4, respectively. Complex 1 readily reduces the Cu1+ reagents, CuBr, CuI, and CuO2CMe, to produce the corresponding (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]UX complexes (X = Br, 5; I, 6; O2CMe, 7). X-ray crystallography established complex 7 as the first f element complex containing a monodentate acetate anion. Complex 7 can also be obtained by reaction of (C5Me5)2[iPrNC(Me)NiPr-κ2N,N′]UMe with CO2 at 80 psi. In contrast to the reactions above, 1 reduces TlC5H5 with the unusual loss of (C5Me5) to form (C5Me5)(C5H5)2[iPrNC(Me)NiPr-κ2N,N′]U, 8.