Reaction Chemistry of the U<sup>3+</sup> Metallocene Amidinate (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>[<sup>i</sup>PrNC(Me)N<sup>i</sup>Pr]U Including the Isolation of a Uranium Complex of a Monodentate Acetate
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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 iPrNCNiPr 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.
