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Enriquez AE, Scott BL, Neu MP. Uranium(III)/(IV) nitrile adducts including UI4(N[triple bond]CPh)4, a synthetically useful uranium(IV) complex. Inorg Chem. 2005;44(21):7403-13doi: 10.1021/ic050578f.
Enriquez, A. E., Scott, B. L., & Neu, M. P. (2005). Uranium(III)/(IV) nitrile adducts including UI4(N[triple bond]CPh)4, a synthetically useful uranium(IV) complex. Inorganic chemistry, 44(21), 7403-13. https://doi.org/10.1021/ic050578f
Enriquez, Alejandro E, et al. "Uranium(III)/(IV) nitrile adducts including UI4(N[triple bond]CPh)4, a synthetically useful uranium(IV) complex." Inorganic chemistry vol. 44,21 (2005): 7403-13. doi: https://doi.org/10.1021/ic050578f
Enriquez AE, Scott BL, Neu MP. Uranium(III)/(IV) nitrile adducts including UI4(N[triple bond]CPh)4, a synthetically useful uranium(IV) complex. Inorg Chem. 2005 Oct 17;44(21):7403-13. doi: 10.1021/ic050578f. PMID: 16212366.
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Inorg Chem. 2005 Oct 17;44(21):7403-13. doi: 10.1021/ic050578f.

Uranium(III)/(IV) nitrile adducts including UI4(N[triple bond]CPh)4, a synthetically useful uranium(IV) complex.

Inorganic chemistry

Alejandro E Enriquez, Brian L Scott, Mary P Neu

Affiliations

  1. Actinide, Catalysis, and Separations Chemistry (C-SIC), Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.

PMID: 16212366 DOI: 10.1021/ic050578f

Abstract

The synthesis of complexes used to elucidate an understanding of fundamental An(III) and An(IV) coordination chemistry requires the development of suitable organic-soluble precursors. The reaction of oxide-free uranium metal turnings with 1.3 equivalents of elemental iodine in acetonitrile provided the U(III)/U(IV) complex salt, [U(N[triple bond]CMe)9][UI6][I] (1), in which the U(III) cation is surrounded by nine acetonitrile molecules in a tricapped trigonal prismatic arrangement, a [UI6]2- counterion, and a noncoordinating iodide. The U-N distances for the prismatic and capping nitrogens are 2.55(3) and 2.71(5) A, respectively. The same reaction performed in benzonitrile afforded crystalline UI4(N[triple bond]CPh)4 (3) in 78% isolated yield. In the solid state, 3 shows an eight-coordinate U(IV) atom in a "puckered" square antiprismatic geometry with U-N and U-I distances of 2.56(1) and 3.027(1) A, respectively. This benzonitrile UI4 adduct is a versatile U(IV) synthon that is soluble in methylene chloride, benzonitrile, and tetrahydrofuran, and moderately soluble in toluene and benzene, but decomposes in benzonitrile at 198 degrees C to [UI(N[triple bond]CPh)8][UI]6 (4), a U(III)/U(IV) salt analogous to 1. A toluene slurry of 3 treated with 2.2 equiv of Cp*MgCl.THF (Cp* = pentamethylcyclopentadienide) provided Cp*2UI2(N[triple bond]CPh) (5) in low yields. Single-crystal X-ray structure determination shows that the iodide ligands in 5 are in a rare cis configuration with an acute I-U-I angle of 83.16(7) degrees . Treatment of a methylene chloride solution of 3 with KTp* (Tp* = hydridotris(3,5-dimethylpyrazolylborate)) formed green TpUI3 (6) which was converted to yellow Tp*UI3(N[triple bond]CMe) (7) by rinsing with acetonitrile. Addition of 2.2 equiv of KTp* to a toluene solution of 3 followed by heating at 95 degrees C, filtration, and crystallization led to the isolation of the dinuclear species [Tp*UI(dmpz)]2[mu-O] (9) (dmpz = 3,5-dimethylpyrazolide), presumably formed by hydrolytic cleavage of excess KTp* by adventitious water. The Tp* complexes 6, 7, and 9 were characterized by single-crystal X-ray diffraction, NMR, FT-IR, and optical absorbance spectroscopies.

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