Archives for Chemistry Experiments of C10H16CuO4

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Synthesis and crystal structure of tetra- and hexanuclear uranium(IV) complexes with hexadentate compartmental Schiff-base ligands

Treatment of UCl4 with the hexadentate Schiff bases H 2L? in thf gave the expected [UL?Cl2(thf)] complexes [H2L? = N,N?-bis(3-methoxysalicylidene)-R and R = 2,2-dimethyl-1,3-propanediamine (i = 1), R = 1,3-propanediamine (i = 2), R = 2-amino-benzylamine (i = 3), R = 2-methyl-1,2-propanediamine (i = 4), R = 1,2-phenylenediamine (i = 5)]. The crystal structure of (UL4Cl 2(thf)] (4) shows the metal in a quite perfect pentagonal bipyramidal configuration, with the two Cl atoms in apical positions. Reaction of UCl 4 with H4L? in pyridine did not afford the mononuclear products [U(H2L?)Cl2(py)x] but gave instead polynuclear complexes [H4L? = N,N?-bis(3-hydroxysalicylidene)-R and R = 1,3-propanediamine (i = 6), R = 2-amino-benzylamine (i = 7) or R = 2-methyl-1,2-propanediamine (i = 8)]. In the presence of H4L6 and H4L7 in pyridine, UCl4 was transformed in a serendipitous and reproducible manner into the tetranuclear U(IV) complexes [Hpy]2[U 4(L6)2(H2L6) 2Cl6] (6a) and [Hpy]2[U4(L 7)2(H2L7)2Cl 6][U4(L7)2(H2L 7)2 Cl4(py)2] (7), respectively. Treatment of UCl4 with [Zn(H2L6)] led to the formation of the neutral compound [U4(L6) 2(H2L6)2Cl4(py) 2] (6b). The hexanuclear complex [Hpy]2[U 6(L8)4Cl10(py)4] (8) was obtained by reaction of UCl4 and H4L8. The centrosymmetric crystal structures of 6a·2HpyCl·2py, 6b·6py, 7·16py and 8·6py illustrate the potential of Schiff bases as associating ligands for the design of polynuclear assemblies.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”