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Synthesis and structural characterization of LiI, ZnII, CdII, and HgII complexes containing a fluorinated β-diketiminate ligand

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/j.jorganchem.2012.08.028
  • β-Diketiminate Ligand
  • Coordination
  • Metal Complexes


Abstract The reaction of a fluorinated β-aminoimine compound ArN]C(Me)CH]C(Me)NHAr (1) (Ar = 2,6-F2C6H3) with n-BuLi in coordinating solvents (Et2O and THF) leads to the solvated complexes [HC(CMeNAr)2]Li(Et2O) (2) and [HC(CMeNAr)2]Li(THF) (3), respectively. They exist as momonuclear complexes featuring lithium atoms in a distorted trigonal planar environment. The same reaction, which was then carried out in a non-coordinated solvent (pentane), provided complex [HC(CMeNAr)2]2Li2 (4). It crystallized as a dinuclear complex in the solid state, featuring lithium atoms in a pseudo-tetrahedral coordination environment. Notably, one fluorine atom of each ligand was involved to stabilize the lithium center. Taking complex 2 as the precursor, a series of group 12 metal complexes were prepared via the reaction with MX2 (M = Zn, Cd, Hg; X = Br, I). The diketiminate zinc complexes [HC(CMeNAr)2]Zn(μ-I)2Li(Et2O)2 (5) and [HC(CMeNAr)2]Zn(μ-Br)2Li(Et2O)2 (6) were successfully synthesized and characterized by single crystal X-ray diffraction analysis. When 2 reacted with CdI2, the expected double iodide bridging product [HC(CMeNAr)2]Cd(μ-I)2Li(Et2O)2 (7a) was only generated in a small amount, with the single iodide bridging complex {HC(CMeNAr)2}Cd(I)(μ-I)Li(Et2O)3 (7b) as the major product. These results were unambiguously confirmed by NMR spectroscopy and X-ray crystallography. Next, a mercury complex [HC(CMeNAr)2]Hg(μ-I)2Li(Et2O) (8) was prepared by using HgI2 as the metal source. Additionally, [HC(CMeNAr)2]ZnEt (9) was also obtained by mixing ligand 1 with Et2Zn.

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