Department of Chemistry, University of California Irvine, California 92697-2025, USA.
Inorg Chem. 2010 Feb 15;49(4):1743-9. doi: 10.1021/ic902141f.
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.
三价铀在茂金属酰胺配合环境中的还原化学性质[(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U, 1]已经得到了探索。1 与 PhSSPh 和 2,2'-二硫代吡啶(pySSpy)反应两当量，分别生成[(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U(SPh), 2]和[(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U(Spy), 3]。配合物 2 和 3 也可以通过插入(i)PrN 水平线 C 水平线 N(i)Pr 进入[(C(5)Me(5))(2)UMe(SPh)]和[(C(5)Me(5))(2)UMe(Spy), 4]的甲基中合成。配合物 1 容易还原 Cu(1+)试剂，CuBr、CuI 和 CuO(2)CMe，生成相应的[(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']UX 配合物（X = Br，5；I，6；O(2)CMe，7）。X 射线晶体学确定 7 为含有单齿乙酸根阴离子的第一个 f 元素配合物。7 也可以通过[(C(5)Me(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']UMe 与 CO(2)在 80 psi 下反应得到。与上述反应不同，1 用不寻常的失去(C(5)Me(5))(-)还原 TlC(5)H(5)形成[(C(5)Me(5))(C(5)H(5))(2)[(i)PrNC(Me)N(i)Pr-kappa(2)N,N']U, 8。
