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

Abstract

The reductive chemistry of U(3+) in the metallocene amidinate coordination environment of (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U, 1, has been explored. Two equivalents of 1 react with PhSSPh and 2,2'-dithiopyridine (pySSpy) to produce (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U(SPh), 2, and (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U(Spy), 3, respectively. Complexes 2 and 3 can also be synthesized through insertion of (i)PrN horizontal lineC horizontal lineN(i)Pr into the methyl group in (C(5)Me(5))(2)UMe(SPh) and (C(5)Me(5))(2)UMe(Spy), 4, respectively. Complex 1 readily reduces the Cu(1+) reagents, CuBr, CuI, and CuO(2)CMe, to produce the corresponding (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']UX complexes (X = Br, 5; I, 6; O(2)CMe, 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 (C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']UMe with CO(2) at 80 psi. In contrast to the reactions above, 1 reduces TlC(5)H(5) with the unusual loss of (C(5)Me(5))(-) to form (C(5)Me(5))(C(5)H(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U, 8.